U.S. patent number 10,774,236 [Application Number 15/955,151] was granted by the patent office on 2020-09-15 for urea (multi)-(meth)acrylate (multi)-silane compositions and articles including the same.
This patent grant is currently assigned to 3M INNOVATIVE PROPERTIES, COMPANY. The grantee listed for this patent is 3M INNOVATIVE PROPERTIES COMPANY. Invention is credited to Guy D. Joly, Thomas P. Klun, Christopher S. Lyons, Alan K. Nachtigal, Mark A. Roehrig, Jennifer K. Schnobrich, Joseph C. Spagnola.
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United States Patent |
10,774,236 |
Klun , et al. |
September 15, 2020 |
Urea (multi)-(meth)acrylate (multi)-silane compositions and
articles including the same
Abstract
Urea (multi)-(meth)acrylate (multi)-silane precursor compounds,
synthesized by reaction of (meth)acrylated materials having
isocyanate functionality with aminosilane compounds, either neat or
in a solvent, and optionally with a catalyst, such as a tin
compound, to accelerate the reaction. Also described are articles
including a substrate, a base (co)polymer layer on a major surface
of the substrate, an oxide layer on the base (co)polymer layer; and
a protective (co)polymer layer on the oxide layer, the protective
(co)polymer layer including the reaction product of at least one
urea (multi)-(meth)acrylate (multi)-silane precursor compound
synthesized by reaction of (meth)acrylated materials having
isocyanate functionality with aminosilane compounds. The substrate
may be a (co)polymer film or an electronic device such as an
organic light emitting device, electrophoretic light emitting
device, liquid crystal display, thin film transistor, or
combination thereof. Methods of making the urea
(multi)-(meth)acrylate (multi)-silanes and their use in composite
films and electronic devices are described.
Inventors: |
Klun; Thomas P. (Lakeland,
MN), Nachtigal; Alan K. (Maplewood, MN), Spagnola; Joseph
C. (Woodbury, MN), Roehrig; Mark A. (Stillwater, MN),
Schnobrich; Jennifer K. (St. Paul, MN), Joly; Guy D.
(Shoreview, MN), Lyons; Christopher S. (St. Paul, MN) |
Applicant: |
Name |
City |
State |
Country |
Type |
3M INNOVATIVE PROPERTIES COMPANY |
St. Paul |
MN |
US |
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Assignee: |
3M INNOVATIVE PROPERTIES,
COMPANY (St. Paul, MN)
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Family
ID: |
50068458 |
Appl.
No.: |
15/955,151 |
Filed: |
April 17, 2018 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20180230325 A1 |
Aug 16, 2018 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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14419303 |
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9982160 |
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PCT/US2013/028503 |
Mar 1, 2013 |
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61681023 |
Aug 8, 2012 |
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61681003 |
Aug 8, 2012 |
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61681008 |
Aug 8, 2012 |
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61681051 |
Aug 8, 2012 |
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61680995 |
Aug 8, 2012 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D
133/14 (20130101); C09D 143/04 (20130101); C23C
14/08 (20130101); B05D 3/101 (20130101); C09D
135/02 (20130101); C23C 16/40 (20130101); H01L
51/107 (20130101); B05D 3/067 (20130101); C08F
130/08 (20130101); C23C 14/34 (20130101); C08K
3/34 (20130101); B05D 3/068 (20130101); C09J
133/14 (20130101); H01L 51/448 (20130101); H01L
51/5253 (20130101); C07F 7/1804 (20130101); B05D
1/60 (20130101); C23C 16/44 (20130101); H01L
51/004 (20130101); B32B 27/308 (20130101); C08J
7/0423 (20200101); Y10T 428/31551 (20150401); C09K
2323/051 (20200801); Y10T 428/31609 (20150401); B32B
2307/7242 (20130101); C08J 2333/12 (20130101); Y10T
428/31663 (20150401); B32B 2250/04 (20130101); Y10T
428/31507 (20150401); Y02E 10/549 (20130101); B32B
2307/7244 (20130101) |
Current International
Class: |
C09D
143/04 (20060101); B05D 1/00 (20060101); C09D
133/14 (20060101); C08J 7/04 (20200101); H01L
51/00 (20060101); C07F 7/18 (20060101); B32B
27/30 (20060101); B05D 3/06 (20060101); H01L
51/10 (20060101); H01L 51/44 (20060101); B05D
3/10 (20060101); C08K 3/34 (20060101); C09D
135/02 (20060101); C23C 14/08 (20060101); C23C
14/34 (20060101); C23C 16/40 (20060101); C23C
16/44 (20060101); C08F 130/08 (20060101); H01L
51/52 (20060101); C09J 133/14 (20060101) |
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|
Primary Examiner: Nelson; Michael B
Attorney, Agent or Firm: Baker; James A.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application
Nos. 61/681,003; 61/681,008; 61/681,023; 61/681,051; and
61/680,995, all filed on Aug. 8, 2012, the disclosures of which are
incorporated by reference herein in their entireties.
Claims
The invention claimed is:
1. An article, comprising: a substrate selected from a
(co)polymeric film or an electronic device, the electronic device
further comprising an organic light emitting device (OLED), an
electrophoretic light emitting device, a liquid crystal display, a
thin film transistor, a photovoltaic device, or a combination
thereof; a base (co)polymer layer on a major surface of the
substrate; an oxide layer on the base (co)polymer layer; and a
protective (co)polymer layer on the oxide layer, wherein the
protective (co)polymer layer consists of a reaction product of a
mixture of only a (meth)acrylic compound and at least one urea
(multi)-(meth)acrylate (multi)-silane precursor compound of the
formula: R.sub.S--N(R.sup.5)--C(O)--N(H)--R.sub.A, wherein: R.sub.S
is a silane containing group of the formula:
--R.sup.1--[Si(Y.sub.p)(R.sup.2).sub.3-p].sub.q, wherein: R.sup.1
is a multivalent alkylene, arylene, alkarylene, or aralkylene
group, said alkylene, arylene, alkarylene, or aralkylene groups
optionally containing one or more catenary oxygen atoms, each Y is
a hydrolysable group, R.sup.2 is a monovalent alkyl or aryl group;
p is 1, 2, or 3, and q is 1-5; R.sub.A is a (meth)acryl group
containing group of the formula: R.sup.11-(A).sub.n, wherein:
R.sup.11 is a polyvalent alkylene, arylene, alkarylene, or
aralkylene group, said alkylene, arylene, alkarylene, or aralkylene
groups optionally containing one or more catenary oxygen atoms, A
is a (meth)acryl group comprising the formula:
X.sup.2--C(O)--C(R.sup.3).dbd.CH.sub.2, further wherein: X.sup.2 is
--O, --S, or --NR.sup.3, R.sup.3 is H, or C.sub.1-C.sub.4, and n=1
to 5; R.sup.5 is H, C.sub.1 to C.sub.6 alkyl, C.sub.3 to C.sub.6
cycloalkyl, or R.sub.S, with the proviso that at least one of the
following conditions applies: n is 2 to 5, R.sup.5 is R.sub.S, or q
is 2 to 5; and wherein the (meth)acrylic compound is tricyclodecane
dimethanol diacrylate.
2. The article of claim 1, wherein each hydrolysable group Y is
independently selected from an alkoxy group, an acetate group, an
aryloxy group, and a halogen.
3. The article of claim 2, wherein at least some of the
hydrolysable groups Y are chlorine.
4. The article of claim 1, further comprising a plurality of
alternating layers of the oxide layer and the protective
(co)polymer layer on the base (co)polymer layer.
5. The article of claim 1, wherein the substrate comprises a
flexible transparent (co)polymeric film, optionally wherein the
substrate comprises polyethylene terephthalate (PET), polyethylene
napthalate (PEN), heat stabilized PET, heat stabilized PEN,
polyoxymethylene, polyvinylnaphthalene, polyetheretherketone, a
fluoro(co)polymer, polycarbonate, polymethylmethacrylate, poly
.alpha.-methyl styrene, polysulfone, polyphenylene oxide,
polyetherimide, polyethersulfone, polyamideimide, polyimide,
polyphthalamide, or combinations thereof.
6. The article of claim 1, wherein the base (co)polymer layer
comprises a (meth)acrylate smoothing layer.
7. The article of claim 1, wherein the oxide layer comprises at
least one oxide, nitride, carbide or boride of atomic elements
selected from Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB, or IIB,
metals of Groups IIIB, IVB, or VB, rare-earth metals, or a
combination or mixture thereof.
8. The article of claim 1, further comprising an oxide layer
applied to the protective (co)polymer layer, optionally wherein the
oxide layer comprises silicon aluminum oxide.
9. An electronic article incorporating the article according to
claim 1, wherein the substrate is a (co)polymer film and the
electronic article is selected from a solid state lighting device,
a display device, and combinations thereof.
10. An electronic article according to claim 9, wherein the solid
state lighting device is selected from a semiconductor
light-emitting diode device, an organic light-emitting diode
device, and a polymer light-emitting diode device.
11. An electronic article according to claim 10, wherein the
display device is selected from a liquid crystal display device, an
organic light-emitting display device, and a quantum dot liquid
crystal display device.
Description
FIELD
The present disclosure relates to the preparation of urea
(multi)-(meth)acrylate (multi)-silane compounds and their use in
preparing composite barrier assemblies. More particularly, the
disclosure relates to vapor-deposited protective (co)polymer layers
including the reaction product of at least one urea
(multi)-(meth)acrylate (multi)-silane precursor compound, used in
multilayer composite barrier assemblies in articles and barrier
films.
BACKGROUND
Inorganic or hybrid inorganic/organic layers have been used in thin
films for electrical, packaging and decorative applications. These
layers can provide desired properties such as mechanical strength,
thermal resistance, chemical resistance, abrasion resistance,
moisture barriers, and oxygen barriers. Highly transparent
multilayer barrier coatings have also been developed to protect
sensitive materials from damage due to water vapor. The moisture
sensitive materials can be electronic components such as organic,
inorganic, and hybrid organic/ inorganic semiconductor devices. The
multilayer barrier coatings can be deposited directly on the
moisture sensitive material, or can be deposited on a flexible
transparent substrate such as a (co)polymer film.
Multilayer barrier coatings can be prepared by a variety of
production methods. These methods include liquid coating techniques
such as solution coating, roll coating, dip coating, spray coating,
spin coating; and dry coating techniques such as Chemical Vapor
Deposition (CVD), Plasma Enhanced Chemical Vapor Deposition
(PECVD), sputtering and vacuum processes for thermal evaporation of
solid materials. One approach for multilayer barrier coatings has
been to produce multilayer oxide coatings, such as aluminum oxide
or silicon oxide, interspersed with thin (co)polymer film
protective layers. Each oxide/(co)polymer film pair is often
referred to as a "dyad", and the alternating oxide/(co)polymer
multilayer construction can contain several dyads to provide
adequate protection from moisture and oxygen. Examples of such
transparent multilayer barrier coatings and processes can be found,
for example, in U.S. Pat. No. 5,440,446 (Shaw et al.); U.S. Pat.
No. 5,877,895 (Shaw et al.); U.S. Pat. No. 6,010,751 (Shaw et al.);
U.S. Pat. No. 7,018,713 (Padiyath et al.); and U.S. Pat. No.
6,413,645 (Graff et al.).
SUMMARY
In one aspect, the present disclosure describes compositions of
matter including at least one urea (multi)-(meth)acrylate
(multi)-silane compound of the formula
R.sub.S--N(R.sup.5)--C(O)--N(H)--R.sub.A. R.sub.S is a silane
containing group of the formula
--R.sup.1-[Si(Y.sub.p)(R.sup.2).sub.3-p].sub.q, wherein R.sup.1 is
a multivalent alkylene, arylene, alkarylene, or aralkylene group,
said alkylene, arylene, alkarylene, or aralkylene groups optionally
containing one or more catenary oxygen atoms, each Y is a
hydrolysable group, R.sup.2 is a monovalent alkyl or aryl group; p
is 1, 2, or 3, and q is 1-5. Additionally, R.sub.A is a (meth)acryl
group containing group of the formula R.sup.11-(A)n, in which
R.sup.11 is a polyvalent alkylene, arylene, alkarylene, or
aralkylene group, said alkylene, arylene, alkarylene, or aralkylene
groups optionally containing one or more catenary oxygen atoms, A
is a (meth)acryl group having the formula
X.sup.2--C(O)--C(R.sup.3).dbd.CH.sub.2, wherein X.sup.2 is --O,
--S, or --NR.sup.3, R.sup.3 is H, or C.sub.1-C.sub.4, and n=1 to 5.
R.sup.5 is H, C.sub.1 to C.sub.6 alkyl or cycloalkyl, or R.sub.S,
with the proviso that at least one of the following conditions
applies: n is 2 to 5, R.sup.5 is R.sub.S, or q is 2 to 5.
In any of the foregoing embodiments, each hydrolysable group Y is
independently selected from an alkoxy group, an acetate group, an
aryloxy group, and a halogen. In some particular exemplary
embodiments of the foregoing, at least some of the hydrolysable
groups Y are chlorine.
In another aspect, the present disclosure describes an article
including a substrate selected from a (co)polymeric film or an
electronic device, the electronic device further including an
organic light emitting device (OLED), an electrophoretic light
emitting device, a liquid crystal display, a thin film transistor,
a photovoltaic device, or a combination thereof; an oxide layer on
the base (co)polymer layer; and a protective (co)polymer layer on
the oxide layer, wherein the protective (co)polymer layer comprises
the reaction product of at least one of the foregoing urea
(multi)-(meth)acrylate (multi)-silane precursor compounds of the
formula R.sub.S--N(R.sup.5)--C(O)--N(H)--R.sub.A, as described
above.
In yet another aspect, the present disclosure describes an article
including a substrate selected from a (co)polymeric film or an
electronic device, the electronic device further including an
organic light emitting device (OLED), an electrophoretic light
emitting device, a liquid crystal display, a thin film transistor,
a photovoltaic device, or a combination thereof; a base (co)polymer
layer on a major surface of the substrate, an oxide layer on the
base (co)polymer layer; and a protective (co)polymer layer on the
oxide layer, wherein the protective (co)polymer layer includes the
reaction product of at least one of the foregoing urea
(multi)-(meth)acrylate (multi)-silane precursor compounds of the
formula R.sub.S1--N(R.sup.4)--C(O)--N(H)--R.sub.A1. R.sub.S1 is a
silane containing group of the formula
--R.sup.1d--Si(Y.sub.p)(R.sup.2).sub.3-p, wherein R.sup.1d is a
divalent alkylene, arylene, alkarylene, or aralkylene group, said
alkylene, arylene, alkarylene, or aralkylene groups optionally
containing one or more catenary oxygen atoms, each Y is a
hydrolysable group, R.sup.2 is a monovalent alkyl or aryl group,
and p is 1, 2, or 3. Additionally, R.sup.4 is H, C.sub.1 to C.sub.6
alkyl or C.sub.1 to C.sub.6 cycloalkyl. R.sub.A1 is a (meth)acryl
containing group of the formula R.sup.11d-(A), wherein R.sup.11d is
a divalent alkylene, arylene, alkarylene, or aralkylene group, said
alkylene, arylene, alkarylene, or aralkylene groups optionally
containing one or more catenary oxygen atoms, and A is a
(meth)acryl group comprising the formula
X.sup.2--C(O)--C(R.sup.3).dbd.CH.sub.2, further wherein X.sup.2 is
--O, --S, or --NR.sup.3, and R.sup.3 is H, or C.sub.1-C.sub.4.
In any of the foregoing articles, each hydrolysable group Y is
independently selected from an alkoxy group, an acetate group, an
aryloxy group, and a halogen. In some particular exemplary
embodiments of the foregoing articles, at least some of the
hydrolysable groups Y are chlorine.
In additional exemplary embodiments of any of the foregoing
articles, the articles further include a multiplicity of
alternating layers of the oxide layer and the protective
(co)polymer layer on the base (co)polymer layer. Some exemplary
embodiments of the present disclosure provide composite barrier
assemblies, for example composite barrier films, Thus, in some
exemplary embodiments of any of the foregoing articles, the
substrate includes a flexible transparent (co)polymeric film,
optionally wherein the substrate comprises polyethylene
terephthalate (PET), polyethylene napthalate (PEN), heat stabilized
PET, heat stabilized PEN, polyoxymethylene, polyvinylnaphthalene,
polyetheretherketone, a fluoro(co)polymer, polycarbonate,
polymethylmethacrylate, poly .alpha.-methyl styrene, polysulfone,
polyphenylene oxide, polyetherimide, polyethersulfone,
polyamideimide, polyimide, polyphthalamide, or combinations
thereof. In other exemplary embodiments of any of the foregoing
articles, the base (co)polymer layer includes a (meth)acrylate
smoothing layer.
In further exemplary embodiments of any of the foregoing articles,
the oxide layer includes at least one oxide, nitride, carbide or
boride of atomic elements selected from Groups IIA, IIIA, IVA, VA,
VIA, VIIA, IB, or IIB, metals of Groups IIIB, IVB, or VB,
rare-earth metals, or a combination or mixture thereof. In some
exemplary embodiments of any of the foregoing articles, the
articles further include an oxide layer applied to the protective
(co)polymer layer, optionally wherein the oxide layer includes
silicon aluminum oxide.
In a further aspect, the disclosure describes methods of using a
composite film as described above in an article selected from a
photovoltaic device, a solid state lighting device, a display
device, and combinations thereof. Exemplary solid state lighting
devices include semiconductor light-emitting diodes (SLEDs, more
commonly known as LEDs), organic light-emitting diodes (OLEDs), or
polymer light-emitting diodes (PLEDs). Exemplary display devices
include liquid crystal displays, OLED displays, and quantum dot
displays.
In another aspect, the disclosure describes a process including:
(a) applying a base (co)polymer layer to a major surface of a
substrate, (b) applying an oxide layer on the base (co)polymer
layer, and (c) depositing on the oxide layer a protective
(co)polymer layer, wherein the protective (co)polymer layer
includes a (co)polymer formed as the reaction product of at least
one of the foregoing urea (multi)-(meth)acrylate (multi)-silane
precursor compounds of the formula
R.sub.S--N(R.sup.5)--C(O)--N(H)--R.sub.A or
R.sub.S1--N(R.sup.4)--C(O)--N(H)--R.sub.A1, as previously
described. The substrate is selected from a (co)polymeric film or
an electronic device, the electronic device further including an
organic light emitting device (OLED), an electrophoretic light
emitting device, a liquid crystal display, a thin film transistor,
a photovoltaic device, or a combination thereof.
In some exemplary embodiments of the process, the at least one urea
(multi)-(meth)acrylate (multi)-silane precursor compound undergoes
a chemical reaction to form the protective (co)polymer layer at
least in part on the oxide layer. Optionally, the chemical reaction
is selected from a free radical polymerization reaction, and a
hydrolysis reaction. In any of the foregoing processes, each
hydrolysable group Y is independently selected from an alkoxy
group, an acetate group, an aryloxy group, and a halogen. In some
particular exemplary embodiments of the foregoing articles, at
least some of the hydrolysable groups Y are chlorine.
In some particular exemplary embodiments of any of the foregoing
processes, step (a) includes (i) evaporating a base (co)polymer
precursor, (ii) condensing the evaporated base (co)polymer
precursor onto the substrate, and (iii) curing the evaporated base
(co)polymer precursor to form the base (co)polymer layer. In
certain such exemplary embodiments, the base (co)polymer precursor
includes a (meth)acrylate monomer.
In certain particular exemplary embodiments of any of the foregoing
processes, step (b) includes depositing an oxide onto the base
(co)polymer layer to form the oxide layer. Depositing is achieved
using sputter deposition, reactive sputtering, chemical vapor
deposition, or a combination thereof. In some particular exemplary
embodiments of any of the foregoing processes, step (b) includes
applying a layer of an inorganic silicon aluminum oxide to the base
(co)polymer layer. In further exemplary embodiments of any of the
foregoing processes, the process further includes sequentially
repeating steps (b) and (c) to form a multiplicity of alternating
layers of the protective (co)polymer layer and the oxide layer on
the base (co)polymer layer.
In additional exemplary embodiments of any of the foregoing
processes, step (c) further includes at least one of co-evaporating
the at least one urea (multi)-(meth)acrylate (multi)-silane
precursor compound with a (meth)acrylate compound from a liquid
mixture, or sequentially evaporating the at least one urea
(multi)-(meth)acrylate (multi)-silane precursor compound and a
(meth)acrylate compound from separate liquid sources. Optionally,
the liquid mixture includes no more than about 10 wt. % of the urea
(multi)-(meth)acrylate (multi)-silane precursor compound. In
further exemplary embodiments of such processes, step (c) further
includes at least one of co-condensing the urea
(multi)-(meth)acrylate (multi)-silane precursor compound with the
(meth)acrylate compound onto the oxide layer, or sequentially
condensing the urea (multi)-(meth)acrylate (multi)-silane precursor
compound and the (meth)acrylate compound on the oxide layer.
In further exemplary embodiments of any of the foregoing processes,
reacting the urea (multi)-(meth)acrylate (multi)-silane precursor
compound with the (meth)acrylate compound to form a protective
(co)polymer layer on the oxide layer occurs at least in part on the
oxide layer.
Some exemplary embodiments of the present disclosure provide
composite barrier assemblies, articles or barrier films which
exhibit improved moisture resistance when used in moisture exposure
applications. Exemplary embodiments of the disclosure can enable
the formation of barrier assemblies, articles or barrier films that
exhibit superior mechanical properties such as elasticity and
flexibility yet still have low oxygen or water vapor transmission
rates.
Exemplary embodiments of barrier assemblies or barrier films
according to the present disclosure are preferably transmissive to
both visible and infrared light. Exemplary embodiments of barrier
assemblies or barrier films according to the present disclosure are
also typically flexible. Exemplary embodiments of barrier
assemblies barrier films according to the present disclosure
generally do not exhibit delamination or curl that can arise from
thermal stresses or shrinkage in a multilayer structure. The
properties of exemplary embodiments of barrier assemblies or
barrier films disclosed herein typically are maintained even after
high temperature and humidity aging.
Various aspects and advantages of exemplary embodiments of the
disclosure have been summarized. The above Summary is not intended
to describe each illustrated embodiment or every implementation of
the present certain exemplary embodiments of the present
disclosure. The Drawings and the Detailed Description that follow
more particularly exemplify certain preferred embodiments using the
principles disclosed herein.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings are incorporated in and constitute a part
of this specification and, together with the description, explain
the advantages and principles of exemplary embodiments of the
present disclosure.
FIG. 1 is a diagram illustrating an exemplary moisture-resistant
barrier assembly in an article or film having a vapor-deposited
adhesion-promoting coating according to an exemplary embodiment of
the present disclosure; and
FIG. 2 is a diagram illustrating an exemplary process and apparatus
for making a barrier film according to an exemplary embodiment of
the present disclosure.
Like reference numerals in the drawings indicate like elements. The
drawings herein are not drawn to scale, and in the drawings, the
illustrated elements are sized to emphasize selected features.
DETAILED DESCRIPTION
Glossary
Certain terms are used throughout the description and the claims
that, while for the most part are well known, may require some
explanation. It should understood that, as used herein,
The words "a", "an", and "the" are used interchangeably with "at
least one" to mean one or more of the elements being described.
By using words of orientation such as "atop", "on", "covering",
"uppermost", "underlying" and the like for the location of various
elements in the disclosed coated articles, we refer to the relative
position of an element with respect to a horizontally-disposed,
upwardly-facing substrate. It is not intended that the substrate or
articles should have any particular orientation in space during or
after manufacture.
By using the term "overcoated" to describe the position of a layer
with respect to a substrate or other element of a barrier assembly
in an article or film of the disclosure, we refer to the layer as
being atop the substrate or other element, but not necessarily
contiguous to either the substrate or the other element.
By using the term "separated by" to describe the position of a
(co)polymer layer with respect to two inorganic barrier layers, we
refer to the (co)polymer layer as being between the inorganic
barrier layers but not necessarily contiguous to either inorganic
barrier layer.
The terms "barrier assembly," "barrier film" or "barrier layer"
refers to an assembly, film or layer which is designed to be
impervious to vapor, gas or aroma migration. Exemplary gases and
vapors that may be excluded include oxygen and/or water vapor.
The term "(meth)acrylate" with respect to a monomer, oligomer or
compound means a vinyl-functional alkyl ester formed as the
reaction product of an alcohol with an acrylic or a methacrylic
acid.
The term "polymer" or "(co)polymer" includes homopolymers and
copolymers, as well as homopolymers or copolymers that may be
formed in a miscible blend, e.g., by coextrusion or by reaction,
including, e.g., transesterification. The term "copolymer" includes
both random and block copolymers.
The term "cure" refers to a process that causes a chemical change,
e.g., a reaction via consumption of water, to solidify a film layer
or increase its viscosity.
The term "cross-linked" (co)polymer refers to a (co)polymer whose
(co)polymer chains are joined together by covalent chemical bonds,
usually via cross-linking molecules or groups, to form a network
(co)polymer. A cross-linked (co)polymer is generally characterized
by insolubility, but may be swellable in the presence of an
appropriate solvent.
The term "cured (co)polymer" includes both cross-linked and
uncross-linked (co)polymers.
The term "T.sub.g" refer to the glass transition temperature of a
cured (co)polymer when evaluated in bulk rather than in a thin film
form. In instances where a (co)polymer can only be examined in thin
film form, the bulk form T.sub.g can usually be estimated with
reasonable accuracy. Bulk form T.sub.g values usually are
determined by evaluating the rate of heat flow vs. temperature
using differential scanning calorimetry (DSC) to determine the
onset of segmental mobility for the (co)polymer and the inflection
point (usually a second-order transition) at which the (co)polymer
can be said to change from a glassy to a rubbery state. Bulk form
T.sub.g values can also be estimated using a dynamic mechanical
thermal analysis (DMTA) technique, which measures the change in the
modulus of the (co)polymer as a function of temperature and
frequency of vibration.
By using the term "visible light-transmissive" support, layer,
assembly or device, we mean that the support, layer, assembly or
device has an average transmission over the visible portion of the
spectrum, T.sub.vis, of at least about 20%, measured along the
normal axis.
The term "metal" includes a pure metal (i.e. a metal in elemental
form such as, for example silver, gold, platinum, and the like) or
a metal alloy.
The term "vapor coating" or "vapor depositing" means applying a
coating to a substrate surface from a vapor phase, for example, by
evaporating and subsequently depositing onto the substrate surface
a precursor material to the coating or the coating material itself.
Exemplary vapor coating processes include, for example, physical
vapor deposition (PVD), chemical vapor deposition (CVD), and
combinations thereof.
Various exemplary embodiments of the disclosure will now be
described with particular reference to the Drawings. Exemplary
embodiments of the present disclosure may take on various
modifications and alterations without departing from the spirit and
scope of the disclosure. Accordingly, it is to be understood that
the embodiments of the present disclosure are not to be limited to
the following described exemplary embodiments, but are to be
controlled by the limitations set forth in the claims and any
equivalents thereof.
Identification of a Problem to be Solved
Flexible barrier assemblies or films are desirable for electronic
devices whose components are sensitive to the ingress of water
vapor. A multilayer barrier assembly or film may provide advantages
over glass as it is flexible, light-weight, durable, and enables
low cost continuous roll-to-roll processing.
Each of the known methods for producing a multilayer barrier
assembly or film has limitations. Chemical deposition methods (CVD
and PECVD) form vaporized metal alkoxide precursors that undergo a
reaction, when adsorbed on a substrate, to form inorganic coatings.
These processes are generally limited to low deposition rates (and
consequently low line speeds), and make inefficient use of the
alkoxide precursor (much of the alkoxide vapor is not incorporated
into the coating). The CVD process also requires high substrate
temperatures, often in the range of 300-500.degree. C., which may
not be suitable for (co)polymer substrates.
Vacuum processes such as thermal evaporation of solid materials
(e.g., resistive heating or e-beam heating) also provide low metal
oxide deposition rates. Thermal evaporation is difficult to scale
up for roll wide web applications requiring very uniform coatings
(e.g., optical coatings) and can require substrate heating to
obtain quality coatings. Additionally, evaporation/sublimation
processes can require ion-assist, which is generally limited to
small areas, to improve the coating quality.
Sputtering has also been used to form metal oxide layers. While the
deposition energy of the sputter process used for forming the
barrier oxide layer is generally high, the energy involved in
depositing the (meth)acrylate layers is generally low. As a result
the (meth)acrylate layer typically does not have good adhesive
properties with the layer below it, for example, an inorganic
barrier oxide sub-layer. To increase the adhesion level of the
protective (meth)acrylate layer to the barrier oxide, a thin
sputtered layer of silicon sub-oxide is known to be useful in the
art. If the silicon sub oxide layer is not included in the stack,
the protective (meth)acrylate layer has poor initial adhesion to
the barrier oxide. The silicon sub oxide layer sputter process must
be carried out with precise power and gas flow settings to maintain
adhesion performance. This deposition process has historically been
susceptible to noise resulting in varied and low adhesion of the
protective (meth)acrylate layer. It is therefore desirable to
eliminate the need for a silicon sub oxide layer in the final
barrier construct for increased adhesion robustness and reduction
of process complexity.
Even when the "as deposited" adhesion of the standard barrier stack
is initially acceptable, the sub oxide and protective
(meth)acrylate layer has demonstrated weakness when exposed to
accelerated aging conditions of 85.degree. C./85% relative humidity
(RH). This inter-layer weakness can result in premature
delamination of the barrier assembly in an article or film from the
devices it is intended to protect. It is desirable that the
multi-layer construction improves upon and maintains initial
adhesion levels when aged in 85.degree. C. and 85% RH.
One solution to this problem is to use what is referred to as a
"tie" layer of particular elements such chromium, zirconium,
titanium, silicon and the like, which are often sputter deposited
as a mono- or thin-layer of the material either as the element or
in the presence of small amount of oxygen. The tie layer element
can then form chemical bonds to both the substrate layer, an oxide,
and the capping layer, a (co)polymer.
Tie layers are generally used in the vacuum coating industry to
achieve adhesion between layers of differing materials. The process
used to deposit the layers often requires fine tuning to achieve
the right layer concentration of tie layer atoms. The deposition
can be affected by slight variations in the vacuum coating process
such as fluctuation in vacuum pressure, out-gassing, and cross
contamination from other processes resulting in variation of
adhesion levels in the product. In addition, tie layers often do
not retain their initial adhesion levels after exposure to water
vapor. A more robust solution for adhesion improvement in a barrier
assembly in an article or film is desirable.
Discovery of a Solution to the Problem
We have surprisingly discovered that a composite barrier assembly
or film comprising a protective (co)polymer layer comprising the
reaction product of at least one urea (multi)-(meth)acrylate
(multi)-silane precursor compound as described further below,
improves the adhesion and moisture barrier performance of a
multilayer composite barrier assembly in an article or film. These
multilayer composite barrier assemblies or barrier films have a
number of applications in the photovoltaic, display, lighting, and
electronic device markets as flexible replacements for glass
encapsulating materials.
In exemplary embodiments of the present disclosure, the desired
technical effects and solution to the technical problem to obtain
improved multilayer composite barrier assemblies or films were
obtained by chemically modifying the compositions used in the
process for applying (e.g., by vapor coating) a protective
(co)polymer layer to a multilayer composite barrier assembly in an
article or film to achieve, in some exemplary embodiments: 1) a
robust chemical bond with an inorganic oxide surface, 2) a robust
chemical bond to the (meth)acrylate coating through
(co)polymerization, and 3) the maintenance of some of the physical
properties of the modified molecules (e.g., boiling point, vapor
pressure, and the like) such that they can be co-evaporated with a
bulk (meth)acrylate material. Multilayer Composite Barrier
Assemblies or Films
Thus, in exemplary embodiments, the disclosure describes a
multilayer composite barrier assembly in an article or film
comprising a substrate, a base (co)polymer layer on a major surface
of the substrate, an oxide layer on the base (co)polymer layer; and
a protective (co)polymer layer on the oxide layer, the protective
(co)polymer layer comprising the reaction product of at least one
urea (multi)-(meth)acrylate (multi)-silane precursor compound
having the general formula
R.sub.A--NH--C(O)--N(R.sup.4)--R.sup.11--[O--C(O)NH--R.sub.S].sub.n,
or
R.sub.S--NH--C(O)--N(R.sup.4)--R.sup.11--[O--C(O)NH--R.sub.A].sub.n,
as described further below. The substrate is selected from a
(co)polymeric film or an electronic device, the electronic device
further including an organic light emitting device (OLED), an
electrophoretic light emitting device, a liquid crystal display, a
thin film transistor, a photovoltaic device, or a combination
thereof.
As further explained below, materials of this type may be
synthesized by reaction of (meth)acrylated materials having
isocyanate functionality with aminosilane compounds, either neat or
in a solvent, and optionally with a catalyst, such as a tin
compound, to accelerate the reaction.
Turning to the drawings, FIG. 1 is a diagram of an exemplary
barrier assembly in an article assembly in an article or film 10
having a moisture resistant coating comprising a single dyad.
Barrier assembly in an article or film 10 includes layers arranged
in the following order: a substrate 12; a base (co)polymer layer
14; an oxide layer 16; a protective (co)polymer layer 18 comprising
the reaction product of at least one urea (multi)-(meth)acrylate
(multi)-silane precursor compound as described herein; and an
optional oxide layer 20. Oxide layer 16 and protective (co)polymer
layer 18 together form a dyad and, although only one dyad is shown,
film 10 can include additional dyads of alternating oxide layer 16
and protective (co)polymer layer 18 between substrate 10 and the
uppermost dyad.
In certain exemplary embodiments, the composite barrier assembly in
an article or film comprises a plurality of alternating layers of
the oxide layer and the protective (co)polymer layer on the base
(co)polymer layer. The oxide layer and protective (co)polymer layer
together form a "dyad", and in one exemplary embodiment, the
barrier assembly in an article or film can include more than one
dyad, forming a multilayer barrier assembly in an article or film.
Each of the oxide layers and/or protective (co)polymer layers in
the multilayer barrier assembly in an article or film (i.e.
including more than one dyad) can be the same or different. An
optional inorganic layer, which preferably is an oxide layer, can
be applied over the plurality of alternating layers or dyads.
In some exemplary embodiments, protective (co)polymer layer 18
comprising the reaction product of at least one urea
(multi)-(meth)acrylate (multi)-silane precursor compound improves
the moisture resistance of film 10 and the peel strength adhesion
of protective (co)polymer layer 18 to the underlying oxide layer,
leading to improved adhesion and delamination resistance within the
further barrier stack layers, as explained further below. Presently
preferred materials for use in the barrier assembly in an article
or film 10 are also identified further below, and in the
Examples.
Protective Polymer Layers
The present disclosure describes protective (co)polymer layers used
in composite barrier assemblies or films (i.e. as barrier films)
useful in reducing oxygen and/or water vapor barrier transmission
when used as packaging materials, for example, to package
electronic devices. Each protective (co)polymer layer includes in
its manufacture at least one composition of matter described herein
as a urea (multi)-(meth)acrylate (multi)-silane precursor compound,
the reaction product thereof forms a (co)polymer, as described
further below.
Thus, in some exemplary embodiments, the present disclosure
describes a composite barrier assembly or film comprising a
substrate, a base (co)polymer layer on a major surface of the
substrate, an oxide layer on the base (co)polymer layer, and a
protective (co)polymer layer on the oxide layer, wherein the
protective (co)polymer layer comprises the reaction product of at
least one of the foregoing urea (multi)-(meth)acrylate
(multi)-silane precursor compounds of the formula
R.sub.S--N(R.sup.5)--C(O)--N(H)--R.sub.A, as described further
below.
In other exemplary embodiments, the present disclosure describes a
composite barrier assembly in an article or film including a
substrate, a base (co)polymer layer on a major surface of the
substrate, an oxide layer on the base (co)polymer layer, and a
protective (co)polymer layer on the oxide layer, wherein the
protective (co)polymer layer includes the reaction product of at
least one of the foregoing urea (multi)-(meth)acrylate
(multi)-silane precursor compounds of the formula
R.sub.S1--N(R.sup.4)--C(O)--N(H)--R.sub.A1. R.sub.S1 is a silane
containing group of the formula --R.sup.1d--Si(Y.sub.p)
(R.sup.2).sub.3-p, wherein R.sup.1d is a divalent alkylene,
arylene, alkarylene, or aralkylene group, said alkylene, arylene,
alkarylene, or aralkylene groups optionally containing one or more
catenary oxygen atoms, each Y is a hydrolysable group, R.sup.2 is a
monovalent alkyl or aryl group, and p is 1, 2, or 3. Additionally,
R.sup.4 is H, C.sub.1 to C.sub.6 alkyl or C.sub.1 to C.sub.6
cycloalkyl. R.sub.A1 is a (meth)acryl containing group of the
formula R.sup.11d-(A), wherein R.sup.11d is a divalent alkylene,
arylene, alkarylene, or aralkylene group, said alkylene, arylene,
alkarylene, or aralkylene groups optionally containing one or more
catenary oxygen atoms, and A is a (meth)acryl group comprising the
formula X.sup.2--C(O)--C(R.sup.3).dbd.CH.sub.2, further wherein
X.sup.2 is --O, --S, or --NR.sup.3, and R.sup.3 is H, or
C.sub.1-C.sub.4.
In any of the foregoing articles, each hydrolysable group Y is
independently selected from an alkoxy group, an acetate group, an
aryloxy group, and a halogen. In some particular exemplary
embodiments of the foregoing articles, at least some of the
hydrolysable groups Y are chlorine.
Composite Barrier Assembly or Barrier Film Materials
The present disclosure describes protective (co)polymer layers
comprising the reaction product of at least one urea
(multi)-urethane (meth)acrylate-silane precursor compound having
the general formula
R.sub.A--NH--C(O)--N(R.sup.4)--R.sup.11--[O--C(O)NH--R.sub.S].sub.n,
or
R.sub.S--NH--C(O)--N(R.sup.4)--R.sup.11--[O--C(O)NH--R.sub.A].sub.n,
as described further below. Among other things, (co)polymer layers
comprising such reaction product(s) of at least one urea
(multi)-urethane (meth)acrylate-silane precursor compound are
useful for improving the interlayer adhesion of composite barrier
assembly in an article or films.
Urea (Multi)-(Meth)Acrylate (Multi)-Silane Precursor Compounds
The present disclosure also describes new compositions of matter
comprising at least one urea (multi)-(meth)acrylate (multi)-silane
compound of the formula: R.sub.S--N(R.sup.5)--C(O)--N(H)--R.sub.A.
R.sub.S is a silane containing group of the formula
--R.sup.1--[Si(Y.sub.p)(R.sup.2).sub.3-p].sub.q, wherein R.sup.1 is
a multivalent alkylene, arylene, alkarylene, or aralkylene group,
said alkylene, arylene, alkarylene, or aralkylene groups optionally
containing one or more catenary oxygen atoms, each Y is a
hydrolysable group, R.sup.2 is a monovalent alkyl or aryl group; p
is 1, 2, or 3, and q is 1-5. Additionally, R.sub.A is a (meth)acryl
group containing group of the formula R.sup.11-(A).sub.n, in which
R.sup.11 is a polyvalent alkylene, arylene, alkarylene, or
aralkylene group, said alkylene, arylene, alkarylene, or aralkylene
groups optionally containing one or more catenary oxygen atoms, A
is a (meth)acryl group having the formula
X.sup.2--C(O)--C(R.sup.3).dbd.CH.sub.2, wherein X.sup.2 is --O,
--S, or --NR.sup.3, R.sup.3 is H, or C.sub.1-C.sub.4, and n=1 to 5.
R.sup.5 is H, C.sub.1 to C.sub.6 alkyl or cycloalkyl, or R.sub.S,
with the proviso that at least one of the following conditions
applies: n is 2 to 5, R.sup.5 is R.sub.S, or q is 2 to 5.
In any of the foregoing embodiments, each hydrolysable group Y is
independently selected from an alkoxy group, an acetate group, an
aryloxy group, and a halogen. In some particular exemplary
embodiments of the foregoing, at least some of the hydrolysable
groups Y are chlorine.
As further explained below, urea (multi)-(meth)acrylate
(multi)-silane compositions may be synthesized by reaction of
(meth)acrylated materials having isocyanate functionality with
aminosilane compounds, either neat or in a solvent, and optionally
with a catalyst, such as a tin compound, to accelerate the
reaction.
Some of these urea (multi)-(meth)acrylate (multi)-silane
compositions contain only one silane group and only one (meth)acryl
group, and are of the formula:
R.sub.S1--N(R.sup.4)--C(O)--N(H)--R.sub.A1 (1) wherein: R.sub.S1 is
a silane containing group of the formula:
--R.sup.1d--Si(Y.sub.p)(R.sup.2).sub.3-p wherein:
R.sup.1d is a divalent alkylene, arylene, alkarylene, or aralkylene
group, said alkylene, arylene, alkarylene, or aralkylene groups
optionally containing one or more catenary oxygen atoms,
Y is a hydrolysable group, which includes alkoxy groups, acetate
groups, aryloxy groups, and halogens, especially chlorine, and
R.sup.2 is a monovalent alkyl or aryl group, and
p is 1, 2, or 3; R.sub.A1 is a (meth)acryl group containing group
of the formula:
R.sup.11d-(A) wherein:
R.sup.11d is a divalent alkylene, arylene, alkarylene, or
aralkylene group, said alkylene, arylene, alkarylene, or aralkylene
groups optionally containing one or more catenary oxygen atoms,
and
A is a (meth)acryl group comprising the formula
X.sup.2--C(O)--C(R.sup.3).dbd.CH.sub.2: wherein X.sup.2 is --O,
--S, or --NR.sup.3, further wherein R.sup.3 is H, or
C.sub.1-C.sub.4; and R.sup.4 is H, C.sub.1 to C.sub.6 alkyl or
cycloalkyl.
Some of the exemplary urea (multi)-(meth)acrylate (multi)-silane
compositions contain two or more silane groups and/or two or more
(meth)acryl groups, and have the general formula:
R.sub.S--N(R.sup.5)--C(O)--N(H)--R.sub.A (2) wherein: R.sub.S is a
silane containing group of the formula:
--R.sup.1--[Si(Y.sub.p)(R.sup.2).sub.3-p].sub.q wherein:
R.sup.1 is a multivalent alkylene, arylene, alkarylene, or
aralkylene group, said alkylene, arylene, alkarylene, or aralkylene
groups optionally containing one or more catenary oxygen atoms,
Y is a hydrolysable group, which includes alkoxy groups, acetate
groups, aryloxy groups, and halogens, especially chlorine, and
R.sup.2 is a monovalent alkyl or aryl group; and
p is 1, 2, or 3,
q is 1-5 R.sub.A is a (meth)acryl group containing group of the
formula:
R.sup.11-(A).sub.n wherein:
R.sup.11 is a polyvalent alkylene, arylene, alkarylene, or
aralkylene group, said alkylene, arylene, alkarylene, or aralkylene
groups optionally containing one or more catenary oxygen atoms,
A is a (meth)acryl group comprising the formula
X.sup.2--C(O)--C(R.sup.3).dbd.CH.sub.2 wherein:
X.sup.2 is --O, --S, or --NR.sup.3, where R.sup.3 is H, or
C.sub.1-C.sub.4; and n=1 to 5; and R.sup.5 is H, C.sub.1 to C.sub.6
alkyl or cycloalkyl, or R.sub.S, with the proviso that at least one
of the following conditions applies:
n is 2 to 5, R.sup.5 is R.sub.S, or q is 2 to 5.
Some suitable (meth)acrylated materials having mono-isocyanate
functionality include 3-isocyanatoethyl methacrylate,
3-isocyanatoethyl methacrylate, and 1,1-bis(acryloyloxymethyl)
ethyl isocyanate.
Aminosilanes suitable for use in connection with the present
disclosure may be primary or secondary. Some primary aminosilanes
useful in the practice of this disclosure are described in U.S.
Pat. No. 4,378,250 (Treadway et al., incorporated herein by
reference in its entirety) and include aminoethyltriethoxysilane,
.beta.-aminoethyltrimethoxysilane,
.beta.-aminoethyltriethoxysilane, .beta.-aminoethyltributoxysilane,
.beta.-aminoethyltripropoxysilane,
.alpha.-amino-ethyltrimethoxysilane,
.alpha.-aminoethyltriethoxysilane,
.gamma.-aminopropyltrimethoxy-silane,
.gamma.-aminopropyltriethoxysilane,
.gamma.-aminopropyltributoxysilane,
.gamma.-aminopropyl-tripropoxysilane,
.beta.-aminopropyltrimethoxysilane,
.beta.-aminopropyltriethoxysilane,
.beta.-amino-propyltripropoxysilane,
.beta.-aminopropyltributoxysilane,
.alpha.-aminopropyltrimethoxysilane,
.alpha.-aminopropyltriethoxysilane,
.alpha.-aminopropyltributoxysilane, and
.alpha.-aminopropyltri-propoxysilane.
Some secondary aminosilanes useful in the practice of the
disclosure include N-methyl aminopropyltrimethoxysilane, N-methyl
aminopropyltriethoxysilane, bis(propyl-3-trimethoxysilane) amine,
bis(propyl-3-triethoxysilane) amine,
N-butyl-aminopropyltrimethoxysilane, N-butyl
aminopropyltriethoxysilane,
N-cyclohexyl-aminopropyltrimethoxysilane, N-cyclohexyl
aminomethyltrimethoxysilane, N-cyclohexyl
aminomethyltriethoxysilane, and N-cyclohexyl aminomethyldiethoxy-
monomethylsilane.
Typical preparation procedures for urea compounds can be found in
Polyurethanes: Chemistry and Technology, Saunders and Frisch,
Interscience Publishers (New York, 1963 (Part I) and 1964 (Part
II).
The molecular weight of the urea (multi)-(meth)acrylate
(multi)-silane precursor compound is in the range where sufficient
vapor pressure at vacuum process conditions is effective to carry
out evaporation and then subsequent condensation to a thin liquid
film. The molecular weights are preferably less than about 2,000
Da, more preferably less than 1,000 Da, even more preferably less
than 500 Da.
Preferably, the urea (multi)-(meth)acrylate (multi)-silane
precursor compound is present at no more than 20% by weight (% wt.)
of the vapor coated mixture; more preferably no more than 19%, 18%,
17%, 16%, 15%, 14%, 13%, 12%, 11%, and even more preferably 10%,
9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or even 1% wt. of the vapor
deposited mixture.
An optional inorganic layer, which preferably is an oxide layer,
can be applied over the protective (co)polymer layer. Presently
preferred inorganic layers comprise at least one of silicon
aluminum oxide or indium tin oxide.
Substrates
The substrate 12 is selected from a (co)polymeric film or an
electronic device, the electronic device further including an
organic light emitting device (OLED), an electrophoretic light
emitting device, a liquid crystal display, a thin film transistor,
a photovoltaic device, or a combination thereof.
Typically, the electronic device substrate is a moisture sensitive
electronic device. The moisture sensitive electronic device can be,
for example, an organic, inorganic, or hybrid organic/inorganic
semiconductor device including, for example, a photovoltaic device
such as a copper indium gallium (di)selenide (CIGS) solar cell; a
display device such as an organic light emitting display (OLED),
electrochromic display, electrophoretic display, or a liquid
crystal display (LCD) such as a quantum dot LCD display; an OLED or
other electroluminescent solid state lighting device, or
combinations thereof and the like.
In some exemplary embodiments, substrate 12 can be a flexible,
visible light-transmissive substrate, such as a flexible light
transmissive (co)polymeric film. In one presently preferred
exemplary embodiment, the substrates are substantially transparent,
and can have a visible light transmission of at least about 50%,
60%, 70%, 80%, 90% or even up to about 100% at 550 nm.
Exemplary flexible light-transmissive substrates include
thermoplastic polymeric films including, for example, polyesters,
polyacrylates (e.g., polymethyl methacrylate), polycarbonates,
polypropylenes, high or low density polyethylenes, polysulfones,
polyether sulfones, polyurethanes, polyamides, polyvinyl butyral,
polyvinyl chloride, fluoropolymers (e.g., polyvinylidene
difluoride, ethylenetetrafluoroethylene (ETFE) (co)polymers,
terafluoroethylene (co)polymers, hexafluoropropylene (co)polymers,
polytetrafluoroethylene, and copolymers thereof), polyethylene
sulfide, cyclic olefin (co)polymers, and thermoset films such as
epoxies, cellulose derivatives, polyimide, polyimide benzoxazole
and polybenzoxazole.
Presently preferred polymeric films comprise polyethylene
terephthalate (PET), polyethylene napthalate (PEN), heat stabilized
PET, heat stabilized PEN, polyoxymethylene, polyvinylnaphthalene,
polyetheretherketone, fluoropolymer, polycarbonate,
polymethylmethacrylate, poly .alpha.-methyl styrene, polysulfone,
polyphenylene oxide, polyetherimide, polyethersulfone,
polyamideimide, polyimide, polyphthalamide, or combinations
thereof.
In some exemplary embodiments, the substrate can also be a
multilayer optical film ("MOF"), such as those described in U.S.
Patent Application Publication No. US 2004/0032658 A1. In one
exemplary embodiment, the films can be prepared on a substrate
including PET.
The substrate may have a variety of thicknesses, e.g., about 0.01
to about 1 mm. The substrate may however be considerably thicker,
for example, when a self-supporting article is desired. Such
articles can conveniently also be made by laminating or otherwise
joining a disclosed film made using a flexible substrate to a
thicker, inflexible or less flexible supplemental support.
The (co)polymeric film can be heat-stabilized, using heat setting,
annealing under tension, or other techniques that will discourage
shrinkage up to at least the heat stabilization temperature when
the (co)polymeric film is not constrained.
Base (Co)polymer Layer
Returning to FIG. 1, the base (co)polymer layer 14 can include any
(co)polymer suitable for deposition in a thin film. In one aspect,
for example, the base (co)polymer layer 14 can be formed from
various precursors, for example, (meth)acrylate monomers and/or
oligomers that include acrylates or methacrylates such as urethane
(meth)acrylates, isobornyl (meth)acrylate, dipentaerythritol
penta(meth)acrylate, epoxy (meth)acrylates, epoxy (meth)acrylates
blended with styrene, di-trimethylolpropane tetra(meth)acrylate,
diethylene glycol di(meth)acrylate, 1,3-butylene glycol
di(meth)acrylate, penta(meth)acrylate esters, pentaerythritol
tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated
(3) trimethylolpropane tri(meth)acrylate, ethoxylated (3)
trimethylolpropane tri(meth)acrylate, alkoxylated trifunctional
(meth)acrylate esters, dipropylene glycol di(meth)acrylate,
neopentyl glycol di(meth)acrylate, ethoxylated (4) bisphenol a
di(metha)crylate, cyclohexane dimethanol di(meth)acrylate esters,
isobornyl (meth)acrylate, cyclic di(meth)acrylates, tris (2-hydroxy
ethyl) isocyanurate tri(meth)acrylate, and (meth)acrylate compounds
(e.g., oligomers or polymers) formed from the foregoing acrylates
and methacrylates. Preferably, the base (co)polymer precursor
comprises a (meth)acrylate monomer.
The base (co)polymer layer 14 can be formed by applying a layer of
a monomer or oligomer to the substrate and cross-linking the layer
to form the (co)polymer in situ, e.g., by flash evaporation and
vapor deposition of a radiation-cross-linkable monomer, followed by
cross-linking using, for example, an electron beam apparatus, UV
light source, electrical discharge apparatus or other suitable
device. Coating efficiency can be improved by cooling the
substrate.
The monomer or oligomer can also be applied to the substrate 12
using conventional coating methods such as roll coating (e.g.,
gravure roll coating) or spray coating (e.g., electrostatic spray
coating), then cross-linked as set out above. The base (co)polymer
layer 14 can also be formed by applying a layer containing an
oligomer or (co)polymer in solvent and drying the thus-applied
layer to remove the solvent. Chemical Vapor Deposition (CVD) may
also be employed in some cases.
Preferably, the base (co)polymer layer 14 is formed by flash
evaporation and vapor deposition followed by crosslinking in situ,
e.g., as described in U.S. Patent No. 4,696,719 (Bischoff), U.S.
Pat. No. 4,722,515 (Ham), U.S. Pat. No. 4,842,893 (Yializis et
al.), U.S. Pat. No. 4,954,371 (Yializis), U.S. Pat. No. 5,018,048
(Shaw et al.), U.S. Pat. No. 5,032,461(Shaw et al.), U.S. Pat. No.
5,097,800 (Shaw et al.), U.S. Pat. No. 5,125,138 (Shaw et al.),
U.S. Pat. No. 5,440,446 (Shaw et al.), U.S. Pat. No. 5,547,908
(Furuzawa et al.), U.S. Pat. No. 6,045,864 (Lyons et al.), U.S.
Pat. No. 6,231,939 (Shaw et al. and U.S. Pat. No. 6,214,422
(Yializis); in PCT International Publication No. WO 00/26973 (Delta
V Technologies, Inc.); in D. G. Shaw and M. G. Langlois, "A New
Vapor Deposition Process for Coating Paper and Polymer Webs", 6th
International Vacuum Coating Conference (1992); in D. G. Shaw and
M. G. Langlois, "A New High Speed Process for Vapor Depositing
Acrylate Thin Films: An Update", Society of Vacuum Coaters 36th
Annual Technical Conference Proceedings (1993); in D. G. Shaw and
M. G. Langlois, "Use of Vapor Deposited Acrylate Coatings to
Improve the Barrier Properties of Metallized Film", Society of
Vacuum Coaters 37th Annual Technical Conference Proceedings (1994);
in D. G. Shaw, M. Roehrig, M. G. Langlois and C. Sheehan, "Use of
Evaporated Acrylate Coatings to Smooth the Surface of Polyester and
Polypropylene Film Substrates", RadTech (1996); in J. Affinito, P.
Martin, M. Gross, C. Coronado and E. Greenwell, "Vacuum Deposited
Polymer/Metal Multilayer Films for Optical Application", Thin Solid
Films 270, 43-48 (1995); and in J. D. Affinito, M. E. Gross, C. A.
Coronado, G. L. Graff, E. N. Greenwell and P. M. Martin,
"Polymer-Oxide Transparent Barrier Layers", Society of Vacuum
Coaters 39th Annual Technical Conference Proceedings (1996).
In some exemplary embodiments, the smoothness and continuity of the
base (co)polymer layer 14 (and also each oxide layer 16 and
protective (co)polymer layer 18) and its adhesion to the underlying
substrate or layer may be enhanced by appropriate pretreatment.
Examples of a suitable pretreatment regimen include an electrical
discharge in the presence of a suitable reactive or non-reactive
atmosphere (e.g., plasma, glow discharge, corona discharge,
dielectric barrier discharge or atmospheric pressure discharge);
chemical pretreatment or flame pretreatment. These pretreatments
help make the surface of the underlying layer more receptive to
formation of the subsequently applied (co)polymeric (or inorganic)
layer. Plasma pretreatment can be particularly useful.
In some exemplary embodiments, a separate adhesion promotion layer
which may have a different composition than the base (co)polymer
layer 14 may also be used atop the substrate or an underlying layer
to improve adhesion. The adhesion promotion layer can be, for
example, a separate (co)polymeric layer or a metal-containing layer
such as a layer of metal, metal oxide, metal nitride or metal
oxynitride. The adhesion promotion layer may have a thickness of a
few nm (e.g., 1 or 2 nm) to about 50 nm, and can be thicker if
desired.
The desired chemical composition and thickness of the base
(co)polymer layer will depend in part on the nature and surface
topography of the substrate. The thickness preferably is sufficient
to provide a smooth, defect-free surface to which the subsequent
oxide layer can be applied. For example, the base (co)polymer layer
may have a thickness of a few nm (e.g., 2 or 3 nm) to about 5
micrometers, and can be thicker if desired.
In another aspect, the barrier assembly includes a substrate
selected from a (co)polymer film and a moisture sensitive device,
and the barrier layers are disposed on or adjacent to the
substrate. As described further below, the barrier assembly can be
deposited directly on a (co)polymer film substrate, or a substrate
that includes a moisture sensitive device, a process often referred
to as direct deposition or direct encapsulation. Exemplary direct
deposition processes and barrier assemblies or described in U.S.
Pat. No. 5,654,084 (Affinito); U.S. Pat. No. 6,522,067 (Graff et
al.); U.S. Pat. No. 6,548,912 (Graff et al.); U.S. Pat. No.
6,573,652 (Graff et al.); and U.S. Pat. No. 6,835,950 (Brown et
al.).
In some exemplary embodiments, flexible electronic devices can be
encapsulated directly with the methods described herein. For
example, the devices can be attached to a flexible carrier
substrate, and a mask can be deposited to protect electrical
connections from the inorganic layer(s), (co)polymer layer(s), or
other layer(s)s during their deposition. The inorganic layer(s),
(co)polymeric layer(s), and other layer(s) making up the multilayer
barrier assembly can be deposited as described elsewhere in this
disclosure, and the mask can then be removed, exposing the
electrical connections.
In one exemplary direct deposition or direct encapsulation
embodiment, the moisture sensitive device is a moisture sensitive
electronic device. The moisture sensitive electronic device can be,
for example, an organic, inorganic, or hybrid organic/inorganic
semiconductor device including, for example, a photovoltaic device
such as a copper indium gallium (di)selenide (CIGS) solar cell; a
display device such as an organic light emitting display (OLED),
electrochromic display, electrophoretic display, or a liquid
crystal display (LCD) such as a quantum dot LCD display; an OLED or
other electroluminescent solid state lighting device, or
combinations thereof and the like.
Examples of suitable processes for making a multilayer barrier
assembly and suitable transparent multilayer barrier coatings can
be found, for example, in U.S. Patent No. 5,440,446 (Shaw et al.);
U.S. Pat. No. 5,877,895 (Shaw et al.); U.S. Pat. No. 6,010,751
(Shaw et al.); and U.S. Pat. No. 7,018,713 (Padiyath et al.). In
one presently preferred embodiment, the barrier assembly in an
article or film can be fabricated by deposition of the various
layers onto the substrate, in a roll-to-roll vacuum chamber similar
to the system described in U.S. Patent No. 5,440,446 (Shaw et al.)
and U.S. Pat. No. 7,018,713 (Padiyath, et al.).
It is presently preferred that the base polymer layer 14 is formed
by flash evaporation and vapor deposition followed by crosslinking
in situ, e.g., as described in U.S. Patent No. 4,696,719
(Bischoff), U.S. Pat. No. 4,722,515 (Ham), U.S. Pat. No. 4,842,893
(Yializis et al.), U.S. Pat. No. 4,954,371 (Yializis), U.S. Pat.
No. 5,018,048 (Shaw et al.), U.S. Pat. No. 5,032,461(Shaw et al.),
U.S. Pat. No. 5,097,800 (Shaw et al.), U.S. Pat. No. 5,125,138
(Shaw et al.), U.S. Pat. No. 5,440,446 (Shaw et al.), U.S. Pat. No.
5,547,908 (Furuzawa et al.), U.S. Pat. No. 6,045,864 (Lyons et
al.), U.S. Pat. No. 6,231,939 (Shaw et al. and U.S. Pat. No.
6,214,422 (Yializis); and in PCT International Publication No. WO
00/26973 (Delta V Technologies, Inc.).
Oxide Layers
The improved barrier assembly in an article or film includes at
least one oxide layer 16. The oxide layer preferably comprises at
least one inorganic material. Suitable inorganic materials include
oxides, nitrides, carbides or borides of different atomic elements.
Presently preferred inorganic materials included in the oxide layer
comprise oxides, nitrides, carbides or borides of atomic elements
from Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB, or IIB, metals of
Groups IIIB, IVB, or VB, rare-earth metals, or combinations thereof
In some particular exemplary embodiments, an inorganic layer, more
preferably an inorganic oxide layer, may be applied to the
uppermost protective (co)polymer layer. Preferably, the oxide layer
comprises silicon aluminum oxide or indium tin oxide.
In some exemplary embodiments, the composition of the oxide layer
may change in the thickness direction of the layer, i.e. a gradient
composition. In such exemplary embodiments, the oxide layer
preferably includes at least two inorganic materials, and the ratio
of the two inorganic materials changes throughout the thickness of
the oxide layer. The ratio of two inorganic materials refers to the
relative proportions of each of the inorganic materials. The ratio
can be, for example, a mass ratio, a volume ratio, a concentration
ratio, a molar ratio, a surface area ratio, or an atomic ratio.
The resulting gradient oxide layer is an improvement over
homogeneous, single component layers. Additional benefits in
barrier and optical properties can also be realized when combined
with thin, vacuum deposited protective (co)polymer layers. A
multilayer gradient inorganic-(co)polymer barrier stack can be made
to enhance optical properties as well as barrier properties.
The barrier assembly in an article or film can be fabricated by
deposition of the various layers onto the substrate, in a
roll-to-roll vacuum chamber similar to the system described in U.S.
Patent No. 5,440,446 (Shaw et al.) and U.S. Pat. No. 7,018,713
(Padiyath, et al.). The deposition of the layers can be in-line,
and in a single pass through the system. In some cases, the barrier
assembly in an article or film can pass through the system several
times, to form a multilayer barrier assembly in an article or film
having several dyads.
The first and second inorganic materials can be oxides, nitrides,
carbides or borides of metal or nonmetal atomic elements, or
combinations of metal or nonmetal atomic elements. By "metal or
nonmetal" atomic elements is meant atomic elements selected from
the periodic table Groups IIA, IIIA, IVA, VA, VIA, VIIA, IB, or
IIB, metals of Groups IIIB, IVB, or VB, rare-earth metals, or
combinations thereof. Suitable inorganic materials include, for
example, metal oxides, metal nitrides, metal carbides, metal
oxynitrides, metal oxyborides, and combinations thereof, e.g.,
silicon oxides such as silica, aluminum oxides such as alumina,
titanium oxides such as titania, indium oxides, tin oxides, indium
tin oxide ("ITO"), tantalum oxide, zirconium oxide, niobium oxide,
aluminum nitride, silicon nitride, boron nitride, aluminum
oxynitride, silicon oxynitride, boron oxynitride, zirconium
oxyboride, titanium oxyboride, and combinations thereof. ITO is an
example of a special class of ceramic materials that can become
electrically conducting with the proper selection of the relative
proportions of each elemental constituent. Silicon-aluminum oxide
and indium tin oxide are presently preferred inorganic materials
forming the oxide layer 16.
For purposes of clarity, the oxide layer 16 described in the
following discussion is directed toward a composition of oxides;
however, it is to be understood that the composition can include
any of the oxides, nitrides, carbides, borides, oxynitrides,
oxyborides and the like described above.
In one embodiment of the oxide layer 16, the first inorganic
material is silicon oxide, and the second inorganic material is
aluminum oxide. In this embodiment, the atomic ratio of silicon to
aluminum changes throughout the thickness of the oxide layer, e.g.,
there is more silicon than aluminum near a first surface of the
oxide layer, gradually becoming more aluminum than silicon as the
distance from the first surface increases. In one embodiment, the
atomic ratio of silicon to aluminum can change monotonically as the
distance from the first surface increases, i.e., the ratio either
increases or decreases as the distance from the first surface
increases, but the ratio does not both increase and decrease as the
distance from the first surface increases. In another embodiment,
the ratio does not increase or decrease monotonically, i.e. the
ratio can increase in a first portion, and decrease in a second
portion, as the distance from the first surface increases. In this
embodiment, there can be several increases and decreases in the
ratio as the distance from the first surface increases, and the
ratio is non-monotonic. A change in the inorganic oxide
concentration from one oxide species to another throughout the
thickness of the oxide layer 16 results in improved barrier
performance, as measured by water vapor transmission rate.
In addition to improved barrier properties, the gradient
composition can be made to exhibit other unique optical properties
while retaining improved barrier properties. The gradient change in
composition of the layer produces corresponding change in
refractive index through the layer. The materials can be chosen
such that the refractive index can change from high to low, or vice
versa. For example, going from a high refractive index to a low
refractive index can allow light traveling in one direction to
easily pass through the layer, while light travelling in the
opposite direction may be reflected by the layer. The refractive
index change can be used to design layers to enhance light
extraction from a light emitting device being protected by the
layer. The refractive index change can instead be used to pass
light through the layer and into a light harvesting device such as
a solar cell. Other optical constructions, such as band pass
filters, can also be incorporated into the layer while retaining
improved barrier properties.
In order to promote silane bonding to the oxide surface, it may be
desirable to form hydroxyl silanol (Si--OH) groups on a freshly
sputter deposited silicon dioxide (SiO.sub.2) layer. The amount of
water vapor present in a multi-process vacuum chamber can be
controlled sufficiently to promote the formation of Si--OH groups
in high enough surface concentration to provide increased bonding
sites. With residual gas monitoring and the use of water vapor
sources the amount of water vapor in a vacuum chamber can be
controlled to ensure adequate generation of Si--OH groups.
Process for Making Articles Including Barrier Assemblies or Barrier
Films
In other exemplary embodiments, the disclosure describes a process,
e.g. for making a barrier film on a (co)polymer film substrate or
for making an article by depositing a multilayer composite barrier
assembly on an electronic device substrate, the process including:
(a) applying a base (co)polymer layer to a major surface of a
substrate, (b) applying an oxide layer on the base (co)polymer
layer, and (c) depositing on the oxide layer a protective
(co)polymer layer, wherein the protective (co)polymer layer
comprises a (co)polymer formed as the reaction product of at least
one of the foregoing urea (multi)-(meth)acrylate (multi)-silane
precursor compounds of the formula
R.sub.S--N(R.sup.5)--C(O)--N(H)--R.sub.A or
R.sub.S1--N(R.sup.4)--C(O)--N(H)--R.sub.A1, as previously
described.
In some exemplary embodiments of the process, the at least one urea
(multi)-(meth)acrylate (multi)-silane precursor compound undergoes
a chemical reaction to form the protective (co)polymer layer at
least in part on the oxide layer. Optionally, the chemical reaction
is selected from a free radical polymerization reaction, and a
hydrolysis reaction. In any of the foregoing articles, each
hydrolysable group Y is independently selected from an alkoxy
group, an acetate group, an aryloxy group, and a halogen. In some
particular exemplary embodiments of the foregoing articles, at
least some of the hydrolysable groups Y are chlorine.
In other exemplary embodiments, the disclosure describes a process,
e.g. for making a barrier film on a (co)polymer film substrate or
for making an article by depositing a multilayer composite barrier
assembly on an electronic device substrate, the process including:
(a) vapor depositing and curing a base (co)polymer layer onto a
major surface of a (co)polymer film substrate; (a) vapor depositing
and curing a base (co)polymer layer onto a major surface of a
substrate; (b) vapor depositing an oxide layer on the base
(co)polymer layer; and (c) vapor depositing and curing onto the
oxide layer a protective (co)polymer layer, the protective
(co)polymer layer comprising a (co)polymer formed as the reaction
product of at least one of the foregoing urea
(multi)-(meth)acrylate (multi)-silane precursor compounds of the
formula R.sub.S--N(R.sup.5)--C(O)--N(H)--R.sub.A or
R.sub.S1--N(R.sup.4)--C(O)--N(H)--R.sub.A1, as previously
described.
The vapor deposition process is generally limited to compositions
that are pumpable (liquid-phase with an acceptable viscosity); that
can be atomized (form small droplets of liquid), flash evaporated
(high enough vapor pressure under vacuum conditions), condensable
(vapor pressure, molecular weight), and can be cross-linked in
vacuum (molecular weight range, reactivity, functionality).
FIG. 2 is a diagram of a system 22, illustrating a process for
making barrier assembly in an article or film 10. System 22 is
contained within an inert environment and includes a chilled drum
24 for receiving and moving the substrate 12 (FIG. 1), as
represented by a film 26, thereby providing a moving web on which
to form the barrier layers. Preferably, an optional nitrogen plasma
treatment unit 40 may be used to plasma treat or prime film 26 in
order to improve adhesion of the base (co)polymer layer 14 (FIG. 1)
to substrate 12 (FIG. 1). An evaporator 28 applies a base
(co)polymer precursor, which is cured by curing unit 30 to form
base (co)polymer layer 14 (FIG. 1) as drum 24 advances the film 26
in a direction shown by arrow 25. An oxide sputter unit 32 applies
an oxide to form layer 16 (FIG. 1) as drum 24 advances film 26.
For additional alternating oxide layers 16 and protective
(co)polymer layers 18, drum 24 can rotate in a reverse direction
opposite arrow 25 and then advance film 26 again to apply the
additional alternating base (co)polymer and oxide layers, and that
sub-process can be repeated for as many alternating layers as
desired or needed. Once the base (co)polymer and oxide are
complete, drum 24 further advances the film, and evaporator 36
deposits on oxide layer 16, the urea (multi)-(meth)acrylate
(multi)-silane compound (as described above), which is reacted or
cured to form protective (co)polymer layer 18 (FIG. 1). In certain
presently preferred embodiments, reacting the urea
(multi)-(meth)acrylate (multi)-silane compound to form a protective
(co)polymer layer 18 on the oxide layer 16 occurs at least in part
on the oxide layer 16.
Optional evaporator 34 may be used additionally to provide other
co-reactants or co-monomers (e.g. additional protective (co)polymer
compounds) which may be useful in forming the protective
(co)polymer layer 18 (FIG. 1). For additional alternating oxide
layers 16 and protective (co)polymer layers 18, drum 24 can rotate
in a reverse direction opposite arrow 25 and then advance film 26
again to apply the additional alternating oxide layers 16 and
protective (co)polymer layers 18, and that sub-process can be
repeated for as many alternating layers or dyads as desired or
needed.
The oxide layer 16 can be formed using techniques employed in the
film metalizing art such as sputtering (e.g., cathode or planar
magnetron sputtering), evaporation (e.g., resistive or electron
beam evaporation), chemical vapor deposition, plating and the like.
In one aspect, the oxide layer 16 is formed using sputtering, e.g.,
reactive sputtering. Enhanced barrier properties have been observed
when the oxide layer is formed by a high energy deposition
technique such as sputtering compared to lower energy techniques
such as conventional chemical vapor deposition processes. Without
being bound by theory, it is believed that the enhanced properties
are due to the condensing species arriving at the substrate with
greater kinetic energy as occurs in sputtering, leading to a lower
void fraction as a result of compaction.
In some exemplary embodiments, the sputter deposition process can
use dual targets powered by an alternating current (AC) power
supply in the presence of a gaseous atmosphere having inert and
reactive gasses, for example argon and oxygen, respectively. The AC
power supply alternates the polarity to each of the dual targets
such that for half of the AC cycle one target is the cathode and
the other target is the anode. On the next cycle the polarity
switches between the dual targets. This switching occurs at a set
frequency, for example about 40 kHz, although other frequencies can
be used. Oxygen that is introduced into the process forms oxide
layers on both the substrate receiving the inorganic composition,
and also on the surface of the target. The dielectric oxides can
become charged during sputtering, thereby disrupting the sputter
deposition process. Polarity switching can neutralize the surface
material being sputtered from the targets, and can provide
uniformity and better control of the deposited material.
In further exemplary embodiments, each of the targets used for dual
AC sputtering can include a single metal or nonmetal element, or a
mixture of metal and/or nonmetal elements. A first portion of the
oxide layer closest to the moving substrate is deposited using the
first set of sputtering targets. The substrate then moves proximate
the second set of sputtering targets and a second portion of the
oxide layer is deposited on top of the first portion using the
second set of sputtering targets. The composition of the oxide
layer changes in the thickness direction through the layer.
In additional exemplary embodiments, the sputter deposition process
can use targets powered by direct current (DC) power supplies in
the presence of a gaseous atmosphere having inert and reactive
gasses, for example argon and oxygen, respectively. The DC power
supplies supply power (e.g. pulsed power) to each cathode target
independent of the other power supplies. In this aspect, each
individual cathode target and the corresponding material can be
sputtered at differing levels of power, providing additional
control of composition through the layer thickness. The pulsing
aspect of the DC power supplies is similar to the frequency aspect
in AC sputtering, allowing control of high rate sputtering in the
presence of reactive gas species such as oxygen. Pulsing DC power
supplies allow control of polarity switching, can neutralize the
surface material being sputtered from the targets, and can provide
uniformity and better control of the deposited material.
In one particular exemplary embodiment, improved control during
sputtering can be achieved by using a mixture, or atomic
composition, of elements in each target, for example a target may
include a mixture of aluminum and silicon. In another embodiment,
the relative proportions of the elements in each of the targets can
be different, to readily provide for a varying atomic ratio
throughout the oxide layer. In one embodiment, for example, a first
set of dual AC sputtering targets may include a 90/10 mixture of
silicon and aluminum, and a second set of dual AC sputtering
targets may include a 75/25 mixture of aluminum and silicon. In
this embodiment, a first portion of the oxide layer can be
deposited with the 90% Si/10% Al target, and a second portion can
be deposited with the 75% Al/25% Si target. The resulting oxide
layer has a gradient composition that changes from about 90% Si to
about 25% Si (and conversely from about 10% Al to about 75% Al)
through the thickness of the oxide layer.
In typical dual AC sputtering, homogeneous oxide layers are formed,
and barrier performance from these homogeneous oxide layers suffer
due to defects in the layer at the micro and nano-scale. One cause
of these small scale defects is inherently due to the way the oxide
grows into grain boundary structures, which then propagate through
the thickness of the film. Without being bound by theory, it is
believed several effects contribute to the improved barrier
properties of the gradient composition barriers described herein.
One effect can be that greater densification of the mixed oxides
occurs in the gradient region, and any paths that water vapor could
take through the oxide are blocked by this densification. Another
effect can be that by varying the composition of the oxide
materials, grain boundary formation can be disrupted resulting in a
microstructure of the film that also varies through the thickness
of the oxide layer. Another effect can be that the concentration of
one oxide gradually decreases as the other oxide concentration
increases through the thickness, reducing the probability of
forming small-scale defect sites. The reduction of defect sites can
result in a coating having reduced transmission rates of water
permeation.
In some exemplary embodiments, exemplary films can be subjected to
post-treatments such as heat treatment, ultraviolet (UV) or vacuum
UV (VUV) treatment, or plasma treatment. Heat treatment can be
conducted by passing the film through an oven or directly heating
the film in the coating apparatus, e.g., using infrared heaters or
heating directly on a drum. Heat treatment may for example be
performed at temperatures from about 30.degree. C. to about
200.degree. C., about 35.degree. C. to about 150.degree. C., or
about 40.degree. C. to about 70.degree. C.
Other functional layers or coatings that can be added to the
inorganic or hybrid film include an optional layer or layers to
make the film more rigid. The uppermost layer of the film is
optionally a suitable protective layer, such as optional inorganic
layer 20. If desired, the protective layer can be applied using
conventional coating methods such as roll coating (e.g., gravure
roll coating) or spray coating (e.g., electrostatic spray coating),
then cross-linked using, for example, UV radiation. The protective
layer can also be formed by flash evaporation, vapor deposition and
cross-linking of a monomer as described above. Volatilizable
(meth)acrylate monomers are suitable for use in such a protective
layer. In a specific embodiment, volatilizable (meth)acrylate
monomers are employed.
Methods of Using Barrier Films
In a further aspect, the disclosure describes methods of using a
barrier film made as described above in an article selected from a
solid state lighting device, a display device, and combinations
thereof. Exemplary solid state lighting devices include
semiconductor light-emitting diodes (SLEDs, more commonly known as
LEDs), organic light-emitting diodes (OLEDs), or polymer
light-emitting diodes (PLEDs). Exemplary display devices include
liquid crystal displays, OLED displays, and quantum dot
displays.
Exemplary LEDs are described in U.S. Pat. No. 8,129,205. Exemplary
OLEDs are described in U.S. Pat. Nos. 8,193,698 and 8,221,176.
Exemplary PLEDs are described in U.S. Pat. No. 7,943,062.
Unexpected Results and Advantages
Exemplary barrier assemblies in articles or films of the present
disclosure have a number of applications and advantages in the
display, lighting, and electronic device markets as flexible
replacements for glass encapsulating materials. Thus, certain
exemplary embodiments of the present disclosure provide barrier
assemblies in articles or films which exhibit improved moisture
resistance when used in moisture barrier applications. In some
exemplary embodiments, the barrier assembly can be deposited
directly on a substrate that includes a moisture sensitive device,
a process often referred to as direct encapsulation.
The moisture sensitive device can be, for example, an organic,
inorganic, or hybrid organic/inorganic semiconductor device
including, for example, a photovoltaic device such as a CIGS; a
display device such as an OLED, electrochromic, or an
electrophoretic display; an OLED or other electroluminescent solid
state lighting device, or others. Flexible electronic devices can
be encapsulated directly. For example, the devices can be attached
to a flexible carrier substrate, and a mask can be deposited to
protect electrical connections from the oxide layer deposition. A
base (co)polymer layer and the oxide layer can be deposited as
described above, and the mask can then be removed, exposing the
electrical connections.
Exemplary embodiments of the disclosed methods can enable the
formation of barrier assemblies in articles or films that exhibit
superior mechanical properties such as elasticity and flexibility
yet still have low oxygen or water vapor transmission rates. The
barrier assemblies have at least one inorganic or hybrid
organic/oxide layer or can have additional inorganic or hybrid
organic/oxide layers. In one embodiment, the disclosed barrier
assemblies can have inorganic or hybrid layers alternating with
organic compound, e.g., (co)polymer layers. In another embodiment,
the barrier assemblies can include an inorganic or hybrid material
and an organic compound. Barrier assemblies in an article or film
formed using the disclosed method can have an oxygen transmission
rate (OTR) less than about 1 cc/m.sup.2-day, less than about 0.5
cc/m.sup.2-day, or less than about 0.1 cc/m.sup.2-day. Barrier
assemblies in an article or film formed using the disclosed method
can have an water vapor transmission rate (WVTR) less than about 10
cc/m.sup.2-day, less than about 5 cc/m.sup.2-day, or less than
about 1 cc/m.sup.2-day.
Exemplary embodiments of barrier assemblies and more particularly
barrier films according to the present disclosure are preferably
transmissive to both visible and infrared light. The term
"transmissive to visible and infrared light" as used herein can
mean having an average transmission over the visible and infrared
portion of the spectrum of at least about 75% (in some embodiments
at least about 80, 85, 90, 92, 95, 97, or 98%) measured along the
normal axis. In some embodiments, the visible and infrared
light-transmissive barrier assembly has an average transmission
over a range of 400 nm to 1400 nm of at least about 75% (in some
embodiments at least about 80, 85, 90, 92, 95, 97, or 98%). Visible
and infrared light-transmissive barrier assemblies are those that
do not interfere with absorption of visible and infrared light, for
example, by photovoltaic cells. In some embodiments, the visible
and infrared light-transmissive barrier assembly has an average
transmission over a range wavelengths of light that are useful to a
photovoltaic cell of at least about 75% (in some embodiments at
least about 80, 85, 90, 92, 95, 97, or 98%).
In some exemplary barrier film embodiments, a first and second
(co)polymeric film substrate, pressure sensitive adhesive layer,
and barrier assembly can be selected based on refractive index and
thickness to enhance transmission to visible and infrared
light.
Exemplary barrier assemblies and barrier films according to the
present disclosure are typically flexible. The term "flexible" as
used herein refers to being capable of being formed into a roll. In
some embodiments, the term "flexible" refers to being capable of
being bent around a roll core with a radius of curvature of up to
7.6 centimeters (cm) (3 inches), in some embodiments up to 6.4 cm
(2.5 inches), 5 cm (2 inches), 3.8 cm (1.5 inch), or 2.5 cm (1
inch). In some embodiments, the flexible assembly can be bent
around a radius of curvature of at least 0.635 cm (1/4 inch), 1.3
cm (1/2 inch) or 1.9 cm (3/4 inch).
Exemplary barrier assemblies and barrier films according to the
present disclosure generally do not exhibit delamination or curl
that can arise from thermal stresses or shrinkage in a multilayer
structure. Herein, curl is measured using a curl gauge described in
"Measurement of Web Curl" by Ronald P. Swanson presented in the
2006 AWEB conference proceedings (Association of Industrial
Metallizers, Coaters and Laminators, Applied Web Handling
Conference Proceedings, 2006). According to this method curl can be
measured to the resolution of 0.25 m.sup.-1 curvature. In some
embodiments, barrier assemblies and barrier films according to the
present disclosure exhibit curls of up to 7, 6, 5, 4, or 3
m.sup.-1. From solid mechanics, the curvature of a beam is known to
be proportional to the bending moment applied to it. The magnitude
of bending stress is in turn is known to be proportional to the
bending moment. From these relations the curl of a sample can be
used to compare the residual stress in relative terms. Barrier
assemblies and barrier films also typically exhibit high peel
adhesion to EVA, and other common encapsulants for photovoltaics,
cured on a substrate. The properties of the barrier assemblies and
barrier films disclosed herein typically are maintained even after
high temperature and humidity aging.
Exemplary embodiments of the present disclosure have been described
above and are further illustrated below by way of the following
Examples, which are not to be construed in any way as imposing
limitations upon the scope of the present disclosure. On the
contrary, it is to be clearly understood that resort may be had to
various other embodiments, modifications, and equivalents thereof
which, after reading the description herein, may suggest themselves
to those skilled in the art without departing from the spirit of
the present disclosure and/or the scope of the appended claims.
EXAMPLES
The following examples are intended to illustrate exemplary
embodiments within the scope of this disclosure. All parts,
percentages, and ratios in the examples are by weight, unless noted
otherwise. Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the disclosure are approximations,
the numerical values set forth in the specific examples are
reported as precisely as possible. Any numerical value, however,
inherently contains certain errors necessarily resulting from the
standard deviation found in their respective testing measurements.
At the very least, and not as an attempt to limit the application
of the doctrine of equivalents to the scope of the claims, each
numerical parameter should at least be construed in light of the
number of reported significant digits and by applying ordinary
rounding techniques.
Materials
The following materials, abbreviations, and trade names are used in
the Examples:
90% Si/10% Al targets were obtained from Materion Advanced
Chemicals, Inc., Albuquerque, N. Mex.
ETFE film: Ethylene-tetrafluoroethylene film available from St.
Gobain Performance Plastics, Wayne, N.J. under the trade name
"NORTON.RTM. ETFE."
Table 1 lists the materials used to prepare (multi) (meth)acrylate
(multi) silane compounds according to the foregoing disclosure:
TABLE-US-00001 TABLE 1 Materials Used in the Examples Trade Name
Material Type or Acronym Description (Meth)acrylated material with
BEI 1,1-bis(acryloyloxymethyl) ethyl isocyanate functionality
isocyanate available from CBC America Corp. (Commack, NY)
(Meth)acrylated material with IEA Isocyanatoethyl (meth)acrylate
available isocyanate functionality from CBC America Corp. (Commack,
NY) (Meth)acrylated material with IEM Isocyanatoethyl methacrylate
available isocyanate functionality from CBC America Corp. (Commack,
NY) Catalyst DBTDL Dibutyltin dilaurate available from Sigma
Aldrich, (Milwaukee, WI) Solvent MEK Methyl ethyl ketone available
from EMD Chemicals, Inc. Aminosilane Geniosil XL
N-cyclohexyl-triethoxysilylmethylamine 926 available from Wacker
Silicones (Adrian, MI) Aminosilane Dynasylan
Aminopropyltrimethoxysilane available AMMO from Evonik (Piscataway,
NJ) Aminosilane Dynasylan Aminopropyltriethoxysilane available AMEO
from Evonik (Piscataway, NJ) Aminosilane Dynasylan
bis(3-trimethoxysilylpropyl)amine 1124 available from Evonik
(Piscataway, NJ) Aminosilane Dynasylan
bis(3-triethoxysilylpropyl)amine 1122 available from Evonik
(Piscataway, NJ) Aminosilane Dynasylan N-(n-butyl)-3- 1189
aminopropyltrimethoxysilane available from Evonik (Piscataway, NJ)
Aminosilane -- N-methyl-3- aminopropyltrimethoxysilane available
from SynQuest Labs (Alachua, FL) Cyclic Azasilane Cyclic AZA
N-n-butyl-aza-2,2- Silane 1932.4 dimethoxysilacylopentane available
from Gelest, Inc. (Morrisville, PA)
Solvents and other reagents used were obtained from Sigma-Aldrich
Chemical Company (Milwaukee, Wis.), unless otherwise specified.
Synthesis of Urea (multi)-(Meth)acrylate (multi)-Silane Precursor
Compounds
Preparatory Example 1
A 250 mL roundbottom flask with a stirbar was charged with 40 g
(0.117 mol, 341.55 MW) bis(3-trimethoxysilylpropylamine (Dynasylan
1124) and placed in an ice bath. Via a pressure equalizing addition
funnel, 18.17 g (0.117 mol) isocyanatoethyl methacrylate (IEM) was
added over about 25 min. The ice bath was removed and stirring
continued for another hour and 15 min. At that point a sample was
taken for Fourier Transform Infrared (FTIR) spectroscopic analysis,
with the sample showing no isocyanate peak at 2265 cm.sup.-1. The
product, a clear oil, was then isolated:
##STR00001##
Preparatory Example 2
A 500 mL roundbottom flask equipped with overhead stirrer was
charged with 58.50 g (0.414 mol) of isocyanatoethyl (meth)acrylate
(IEA) in a room temperature water bath under dry air. Via a
dropping funnel, 141.53 g (0.414 mol) of
bis(3-trimethoxysilyl-propyl)amine (Dynasylan 1124) was added over
1.5 hours. At that point a sample was taken for FTIR, with the
sample showing no isocyanate peak at 2265 cm.sup.-1. The substance
was characterized by Proton Fourier Transform Nuclear Magnetic
Resonance (NMR):
##STR00002##
Preparatory Example 3
A 250 mL three necked roundbottom flask equipped with an overhead
stirrer was charged with 12.36 g (0.0517 mol, 239.23 MW)
1,1-bis(acryloyloxymethyl) ethyl isocyanate (BEI), and 176
microliters of a 10% solution of DBTDL in MEK (500 ppm based on the
total weight of reactants). The flask was placed in a 35.degree. C.
oil bath, and 17.64 g (0.517 mol, 341.55 MW)
bis-(3-trimethoxysilylpropyl) amine (Dynasylan 1124) was added to
the reaction via dropping funnel over 1 hour. About 10 min after
the amine addition was complete, a sample was taken for FTIR, with
the sample showing no isocyanate peak at 2265 cm.sup.-1. The
product, a clear oil, was then isolated:
##STR00003##
Preparatory Example 4
An experiment was run similar to Preparatory Example 3, except that
12.85 g (0.72 mol, 179.29 MW) aminopropyltrimethoxysilane
(Dynasylan AMMO) was reacted with 17.15 g (0.72 mol)
1,1-bis(acryloyloxymethyl) ethyl isocyanate (BEI), and 176
microliters of a 10% solution of DBTDL in MEK (500 ppm DBTDL) over
about 45 min to provide a the product as an oil:
##STR00004##
Preparatory Example 5
An experiment was run similar to Preparatory Example 1, except that
22.53 g (0.0529 mol, 425.71 MW) bis(3-triethoxysilylpropylamine
(Dynasylan 1122) was reacted with 7.47 g (0.0529 mol) IEA in the
presence of 35 microliters of a 10% solution of DBTDL in MEK (100
ppm DBTDL) to provide the product:
##STR00005##
Preparatory Example 6
An experiment was run similar to Preparatory Example 1, except that
14.42 g (0.065 mol) of aminopropyltriethoxysilane (Dynasylan AMMO)
was reacted with 15.58 g (0.065 mol) of BEI in the presence of 176
microliters of a 10% solution of DBTDL in MEK (500 ppm DBTDL) to
provide the product:
##STR00006##
Preparatory Example 7
A 200 mL flask equipped with an overhead stirrer was charged with
20.0 g (0.0836 mol) 1,1-bis(acryloyloxymethyl) ethyl isocyanate
(BEI) and 250 microliters of 10% DBTDL and placed under dry air in
a 55.degree. C. oil bath. Then 23.02 g (0.0836 mol) of
N-cyclohexyl-triethoxysilylmethylamine (Geniosil XL 926) was added
via a dropping funnel over 20 min. The mixture was allowed to react
for 1 hour. The product, a clear yellow oil, was then isolated, as
shown below. A sample was taken for FTIR, with the sample showing
no isocyanate peak at 2265 cm.sup.-1.
##STR00007##
Preparatory Example 8
A 250mL roundbottom with stirbar was charged with 40 g (0.223 mol,
179.29 MW) aminopropyltrimethoxysilane (Dynasylan AMMO) and placed
in an ice bath. Via a pressure equalizing addition funnel, 34.61 g
(0.223 mol, 155.15 MW) isocyanatoethyl methacrylate (IEM) was added
over about 25 min. The ice bath was removed and stirring continued
for another hour and 15 min, at which time a sample was taken for
FTIR showing no isocyanate peak at 2265 cm.sup.-1, and the product,
a clear oil, was isolated:
##STR00008##
Preparatory Example 9
In a fashion similar to the preparation of Preparatory Example 8,
40 g (0.170 mol, 235.4 MW)
N-(n-butyl)-3-aminopropyltrimethoxysilane (Dynasylan 1189) was
reacted with 26.36 g (0.170 mol) IEM to provide the product as a
clear oil:
##STR00009##
Preparatory Example 10
In a fashion similar to the preparation of Preparatory Example 8,
44.10 g (0.199 mol, 221.37 MW) aminopropyltriethoxysilane
(Dynasylan AMEO) was reacted with 30.90 g (0.199 mol) IEM to
provide the product as a clear oil (Material would solidify at ice
bath temperatures):
##STR00010##
Preparatory Example 11
In a fashion similar to the preparation of Preparatory Example 8,
41.61 g (0.215 mol, 221.37 MW) N- methyl-aminopropyl
trimethoxysilane was reacted with 33.39 g (0.215 mol) IEM to
provide the product as a clear oil:
##STR00011##
Preparatory Example 12
In a fashion similar to the preparation of Preparatory Example 8,
16.79 g (0.0936 mol, 179.29 MW) aminopropyltrimethoxysilane was
reacted with 13.21 g (0.0936 mol, 141.13 MW) isocyanatoethyl
(meth)acrylate (IEA) to provide the urea product:
##STR00012##
Preparatory Example 13
In a fashion similar to the preparation of Preparatory Example 8,
18.76 g (0.080 mol, 235.4 MW)
N-(n-butyl)-3-aminopropyltrimethoxysilane (Dynasylan 1189) was
reacted with 11.25 g (0.080 mol) IEA to provide the product:
##STR00013##
Preparatory Example 14
In a fashion similar to the preparation of Preparatory Example 8,
18.32 g (0.0827 mol) aminopropyltriethoxysilane was reacted with
11.68 g (0.0827 mol) IEA to provide the product:
##STR00014##
Preparatory Example 15
In a fashion similar to the preparation of Preparatory Example 8,
17.30 g (0.090 mol) N-methyl-aminopropyltrimethoxysilane was
reacted with 12.70 g (0.090 mol) IEA to provide the product:
##STR00015##
Preparatory Example 16
A 100 mL roundbottom was charged with 10.16 g (0.072 mol) IEA, and
35 microliters of 10% DBTDL in MEK (100 ppm DBTDL). Via addition
funnel was added 19.84 g (0.072 mol, 275.46 MW)
N-cyclohexyl-triethoxysilylmethylamine at 55 C over 10 min. After
0.5 hrs of further reaction, FTIR analysis showed no isocyanate
peak and the product was isolated:
##STR00016##
Preparatory Example 17
In a fashion similar to the preparation of Preparatory Example 16,
10.81 g (0.069 mol) IEM was reacted at 55.degree. C. in the
presence of 100 ppm DBTDL with 19.19 g (0.069 mol)
N-cyclohexyl-triethoxysilylmethylamine to provide the product:
##STR00017## Composite Barrier Assembly and Barrier Film
Preparation
Examples of multilayer composite barrier assemblies and barrier
films were made on a vacuum coater similar to the coater described
in U.S. Patent No. 5,440,446 (Shaw et al.) and U.S. Pat. No.
7,018,713 (Padiyath, et al.).
Comparative Example 18 and 25 and Examples 19 through 24 below
relate to forming simulated display or lighting device packaging
modules which were subjected to testing under conditions designed
to simulate aging in an outdoor environment and then subjected to a
peel adhesion test to determine if the urea (multi)-(meth)acrylate
(multi)-silanes of the above examples were effective in improving
peel adhesion. Some procedures common to all these Examples are
presented first.
Multilayer composite barrier assemblies in barrier films according
to the examples below were laminated to a 0.05 mm thick ethylene
tetrafluoroethylene (ETFE) film commercially available as
NORTON.RTM. ETFE from St. Gobain Performance Plastics of Wayne,
N.J., using a 0.05 mm thick pressure sensitive adhesive (PSA)
commercially available as 3M OPTICALLY CLEAR ADHESIVE 8172P from 3M
Company, of St. Paul, Minn. The laminated barrier sheets formed in
each Example below was then placed atop a 0.14 mm thick
polytetrafluoroethylene (PTFE) coated aluminum-foil commercially
available commercially as 8656K61, from McMaster-Carr, Santa Fe
Springs, Calif. with 13 mm wide desiccated edge tape commercially
available as SOLARGAIN Edge Tape SET LP01" from Truseal
Technologies Inc. of Solon, Ohio) placed around the perimeter of
the foil between the barrier sheet and the PTFE.
A 0.38 mm thick encapsulant film commercially available as JURASOL
from JuraFilms of Downer Grove, Ill. and an additional layer of the
laminated barrier sheet were placed on the backside of the foil
with the encapsulant between the barrier sheet and the foil. The
multi-component constructions were vacuum laminated at 150.degree.
C. for 12 min.
Test Methods
Aging Test
Some of the laminated constructions described above were aged for
250 hrs, 500 hours, and in some cases, 1,000 hours in an
environmental chamber set to conditions of 85.degree. C. and 85%
relative humidity (RH).
T-peel Adhesion Test
Unaged and aged barrier sheets were cut away from the PTFE surface
and divided into 1.0 in wide strips for adhesion testing using the
ASTM D1876-08 T-peel test method.
The samples were peeled by a peel tester (commercially available
under the trade designation "INISIGHT 2 SL" with Testworks 4
software from MTS, Eden Prarie, Minn.) with a 10 in/min (25.4
cm/min) peel rate. The reported adhesion value in Newtons per
centimeter (N/cm) is the average of four peel measurements from
1.27 cm to 15.1 cm. The barrier sheets were measured for t-peel
adhesion after 250 hours of 85.degree. C. and 85% relative humidity
and again after 500 and/or 1000 hours of exposure.
Example 18 (Comparative)
This example is comparative in the sense that no coupling agents as
described in Examples 1 through 17 were used. A polyethylene
terephthalate (PET) substrate film was covered with a stack of a
(meth)acrylate smoothing layer, an inorganic silicon aluminum oxide
(SiAlOx) barrier and an (meth)acrylate protective layer. The
individual layers were formed as follows:
(Deposition of the (Meth)acrylate Smoothing Layer)
A 305 meter long roll of 0.127 mm thick by 366 mm wide PET film
commercially available XST 6642 from DuPont of Wilmington, Del. was
loaded into a roll-to-roll vacuum processing chamber. The chamber
was pumped down to a pressure of 1.times.10.sup.-5 Torr. The web
speed was maintained at 4.8 meter/min while maintaining the
backside of the film in contact with a coating drum chilled to
-10.degree. C. With the film in contact with the drum, the film
surface was treated with a nitrogen plasma at 0.02 kW of plasma
power. The film surface was then coated with tricyclodecane
dimethanol diacrylate commercially available as SR-833S from
Sartomer USA, LLC, Exton, Pa.). More specifically, the diacrylate
was degassed under vacuum to a pressure of 20 mTorr prior to
coating, loaded into a syringe pump, and pumped at a flow rate of
1.33 mL/min through an ultrasonic atomizer operated at a frequency
of 60 kHz into a heated vaporization chamber maintained at
260.degree. C. The resulting monomer vapor stream condensed onto
the film surface and was electron beam cross-linked using a
multi-filament electron-beam cure gun operated at 7.0 kV and 4 mA
to form a 720 nm (meth)acrylate layer.
(Deposition of the Inorganic Silicon Aluminum Oxide (SiAlOx)
Barrier)
Immediately after the (meth)acrylate deposition and with the film
still in contact with the drum, a SiAlOx layer was
sputter-deposited atop the (meth)acrylate-coated web surface. Two
alternating current (AC) power supplies were used to control two
pairs of cathodes; with each cathode housing two 90% Si/10% Al
targets commercially available from Materion of Albuquerque, N.
Mex. During sputter deposition, the voltage signal from each power
supply was used as an input for a
proportional-integral-differential control loop to maintain a
predetermined oxygen flow to each cathode. The AC power supplies
sputtered the 90% Si/10% Al targets using 5000 watts of power, with
a gas mixture containing 450 sccm argon and 63 sccm oxygen at a
sputter pressure of 3.5 millitorr. This provided a 30 nm thick
SiAlOx layer deposited atop the (meth)acrylate discussed above.
(Deposition of the (Meth)acrylate Protective Layer)
Immediately after the SiAlOx layer deposition and with the film
still in contact with the drum, an (meth)acrylate protective layer
second was coated and cross-linked on the same web generally using
the same conditions as for the deposition of the smoothing layer,
but with the following exceptions. The electron beam cross-linking
was carried out using a multi-filament electron-beam cure gun
operated at 7 kV and 5 mA. This provided a 720 nm thick
(meth)acrylate layer atop Layer 2.
The resulting three layer stack on the (co)polymeric substrate
exhibited an average spectral transmission T.sub.vis of 87%,
determined by averaging the percent transmission T between 400 nm
and 700 nm, measured at a 0.degree. angle of incidence. A water
vapor transmission rate (WVTR) was measured in accordance with ASTM
F-1249 at 50.degree. C. and 100% relative humidity (RH) using MOCON
PERMATRAN-W.RTM. Model 700 WVTR testing system commercially
available from MOCON, Inc, Minneapolis, Minn.). The result was
below the 0.005 g/m.sup.2/day lower detection limit rate of the
apparatus.
The resulting three layer barrier assembly stack was used to form a
simulated solar module construction as discussed in the section on
general procedures above. These simulated solar modules were
subjected to accelerated aging according to the aging test, and
then the T-peel adhesion was assessed as discussed above. The
results of the T-peel adhesion test are presented in Table 2
below.
Example 19
A polyethylene terephthalate (PET) substrate film was covered with
a stack of an (meth)acrylate smoothing layer, an inorganic silicon
aluminum oxide (SiAlOx) barrier and an (meth)acrylate protective
layer containing the disclosure molecules. The individual layers
were formed as in Comparative Example 18 except during the
formation of the protective layer, instead of 100% tricyclodecane
dimethanol diacrylate SR-833S being used, a mixture of 97% by
weight of tricyclodecane dimethanol diacrylate SR-833S and 3% by
weight of the compound synthesized in Example 2 above was used
instead.
The resulting three layer stack on the (co)polymeric substrate
exhibited an average spectral transmission T.sub.vis=87% and a WVTR
below the 0.005 g/m.sup.2/day, both tested as described in
Comparative Example 18. Then the resulting three layer stack was
used to form a simulated solar module construction as discussed in
the section on general procedures above. These simulated solar
modules were subjected to accelerated aging according to the aging
test, and then the T-peel adhesion was assessed as discussed above.
The results of the T-peel adhesion test are presented in Table 2
below.
Example 20
A polyethylene terephthalate (PET) substrate film was covered with
a stack of an (meth)acrylate smoothing layer, an inorganic silicon
aluminum oxide (SiAlOx) barrier and an (meth)acrylate protective
layer containing the disclosure molecules. The individual layers
were formed as in Comparative Example 18 except during the
formation of the protective layer, instead of 100% tricyclodecane
dimethanol diacrylate SR-833S being used, a mixture of 97% by
weight of tricyclodecane dimethanol diacrylate SR-833S and 3% by
weight of the compound synthesized in Preparatory Example 3 above
was used instead.
The resulting three layer stack on the (co)polymeric substrate
exhibited an average spectral transmission T.sub.vis=87% and a WVTR
below 0.005 g/m.sup.2/day, both tested as described in Comparative
Example 18. Then the resulting three layer stack was used to form a
simulated solar module construction as discussed in the section on
general procedures above. These simulated solar modules were
subjected to accelerated aging according to the aging test, and
then the T-peel adhesion was assessed as discussed above. The
results of the T-peel adhesion test are presented in Table 2
below.
Example 21
A polyethylene terephthalate (PET) substrate film was covered with
a stack of an (meth)acrylate smoothing layer, an inorganic silicon
aluminum oxide (SiAlOx) barrier and an (meth)acrylate protective
layer containing the disclosure molecules. The individual layers
were formed as in Comparative Example 18 except during the
formation of the protective layer, instead of 100% tricyclodecane
dimethanol diacrylate SR-833S being used, a mixture of 97% by
weight of tricyclodecane dimethanol diacrylate SR-833S and 3% by
weight of the compound synthesized in Example 4 above was used
instead.
The resulting three layer stack on the (co)polymeric substrate
exhibited an average spectral transmission T.sub.vis=87% and a WVTR
below 0.005 g/m.sup.2/day, both tested as described in Comparative
Example 18. Then the resulting three layer stack was used to form a
simulated solar module construction as discussed in the section on
general procedures above. These simulated solar modules were
subjected to accelerated aging according to the aging test, and
then the T-peel adhesion was assessed as discussed above. The
results of the T-peel adhesion test are presented in Table 2
below.
Example 22
A polyethylene terephthalate (PET) substrate film was covered with
a stack of an (meth)acrylate smoothing layer, an inorganic silicon
aluminum oxide (SiAlOx) barrier and an (meth)acrylate protective
layer containing the disclosure molecules. The individual layers
were formed as in Comparative Example 18 except during the
formation of the protective layer, instead of 100% tricyclodecane
dimethanol diacrylate SR-833S being used, a mixture of 97% by
weight of tricyclodecane dimethanol diacrylate SR-833S and 3% by
weight of the compound synthesized in Example 12 above was used
instead.
The resulting three layer stack on the (co)polymeric substrate
exhibited an average spectral transmission T.sub.vis=87% and a WVTR
below 0.005 g/m.sup.2/day, both tested as described in Comparative
Example 18. Then the resulting three layer stack was used to form a
simulated solar module construction as discussed in the section on
general procedures above. These simulated solar modules were
subjected to accelerated aging according to the aging test, and
then the T-peel adhesion was assessed as discussed above. The
results of the T-peel adhesion test are presented in Table 2
below.
Example 23
A polyethylene terephthalate (PET) substrate film was covered with
a stack of an (meth)acrylate smoothing layer, an inorganic silicon
aluminum oxide (SiAlOx) barrier and an (meth)acrylate protective
layer containing the disclosure molecules. The individual layers
were formed as in Comparative Example 18 except during the
formation of the protective layer, instead of 100% tricyclodecane
dimethanol diacrylate SR-833S being used, a mixture of 97% by
weight of tricyclodecane dimethanol diacrylate SR-833S and 3% by
weight of the compound synthesized in Example 13 above was used
instead.
The resulting three layer stack on the (co)polymeric substrate
exhibited an average spectral transmission T.sub.vis=87% and a WVTR
below 0.005 g/m.sup.2/day, both tested as described in Comparative
Example 18. Then the resulting three layer stack was used to form a
simulated solar module construction as discussed in the section on
general procedures above. These simulated solar modules were
subjected to accelerated aging according to the aging test, and
then the T-peel adhesion was assessed as discussed above. The
results of the T-peel adhesion test are presented in Table 2
below.
Example 24
A polyethylene terephthalate (PET) substrate film was covered with
a stack of an (meth)acrylate smoothing layer, an inorganic silicon
aluminum oxide (SiAlOx) barrier and an (meth)acrylate protective
layer containing the disclosure molecules. The individual layers
were formed as in Comparative Example 18 except during the
formation of the protective layer, instead of 100% tricyclodecane
dimethanol diacrylate SR-833S being used, a mixture of 97% by
weight of tricyclodecane dimethanol diacrylate SR-833S and 3% by
weight of the compound synthesized in Example 15 above was used
instead.
The resulting three layer stack on the (co)polymeric substrate
exhibited an average spectral transmission T.sub.vis=87% and a WVTR
below 0.005 g/m.sup.2/day, both tested as described in Comparative
Example 18. Then the resulting three layer stack was used to form a
simulated solar module construction as discussed in the section on
general procedures above. These simulated solar modules were
subjected to accelerated aging according to the aging test, and
then the T-peel adhesion was assessed as discussed above. The
results of the T-peel adhesion test are presented in Table 2
below.
Example 25 (Comparative)
A polyethylene terephthalate (PET) substrate film was covered with
a stack of an (meth)acrylate smoothing layer, an inorganic silicon
aluminum oxide (SiAlOx) barrier and an (meth)acrylate protective
layer containing the disclosure molecules. The individual layers
were formed as in Comparative Example 18 except during the
formation of the protective layer, instead of 100% tricyclodecane
dimethanol diacrylate SR-833S being used, a mixture of 97% by
weight of tricyclodecane dimethanol diacrylate SR-833S and 3% by
weight of N-n-butyl-aza-2,2-dimethoxysilacyclopentane (commercially
available from Gelest, Morrisville, Pa., under the product code
1932.4) was used instead.
The resulting three layer stack on the (co)polymeric substrate
exhibited an average spectral transmission T.sub.vis=87% and a WVTR
below 0.005 g/m.sup.2/day, both tested as described in Comparative
Example 18. Then the resulting three layer stack was used to form a
simulated solar module construction as discussed in the section on
general procedures above. These simulated solar modules were
subjected to accelerated aging according to the aging test, and
then the T-peel adhesion was assessed as discussed above. The
results of the T-peel adhesion test are presented in Table 2
below.
TABLE-US-00002 TABLE 2 Test Results for Examples 18-25 T-Peel After
Aging T-Peel After Aging T-Peel 250 Hours 1000 Hours Initial @
85.degree. C./85% RH @ 85.degree. C./85% RH Example (N/cm) (N/cm)
(N/cm) 18 (Comparative) 0.3 0.2 0.2 19 10.7 10.4 11.1 20 10.4 10.1
1.3 21 10.5 10.2 11.7 22 10.3 10.3 11.1 23 10.7 10.5 3.0 24 10.3
10.5 11.2 25 (Comparative) 6.0 10.1 0.4
While the specification has described in detail certain exemplary
embodiments, it will be appreciated that those skilled in the art,
upon attaining an understanding of the foregoing, may readily
conceive of alterations to, variations of, and equivalents to these
embodiments. Accordingly, it should be understood that this
disclosure is not to be unduly limited to the illustrative
embodiments set forth hereinabove. Furthermore, all publications,
published patent applications and issued patents referenced herein
are incorporated by reference in their entirety to the same extent
as if each individual publication or patent was specifically and
individually indicated to be incorporated by reference.
Various exemplary embodiments have been described. These and other
embodiments are within the scope of the following listing of
disclosed embodiments and claims.
* * * * *